Blends of fullerene derivatives, and uses thereof in electronic devices

ABSTRACT

Disclosed are compositions of mixed fullerene derivatives with utility in organic semiconductors, and methods of making and using such compositions. In certain embodiments, the present invention relates to compositions of mixed fullerene derivatives further comprising one or more additional fullerene-based components within specified ranges. In certain other embodiments, the invention relates to methods of producing mixed fullerene derivatives of a specific composition from mixed fullerene starting materials, or pure fullerene derivatives of a specific composition from mixed fullerene derivatives. In yet other embodiments, the invention relates to semiconductors and devices comprising a composition of the invention.

RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.13/218,757, file Aug. 26, 2011, now U.S. Pat. No. 8,435,713, issued May7, 2013, which is a continuation of U.S. patent application Ser. No.12/307,701, filed Nov. 24, 2009, now U.S. Pat. No. 8,076,050, issuedDec. 13, 2011, which claims the benefit of priority to PatentCooperation Treaty Application serial number PCT/US2007/072965, filedJul. 6, 2007, which claims the benefit of priority to U.S. ProvisionalPatent Application Ser. No. 60/818,888 filed Jul. 6, 2006, theentireties of all of which are hereby incorporated by reference.

BACKGROUND OF THE INVENTION

Fullerene Derivatives

Significant progress has been made in the development of thin-filmorganic electronic devices, such as photovoltaic cells, transistors,photodetectors, sensors, and other devices for commercial application.Many of these devices utilize solution-processable semiconductors basedon fullerene derivatives in pure form. The most commonly used fullerenederivative is Phenyl-C₆₁-Butyric-Acid-Methyl-Ester ([60]PCBM) (Scharberet al., Advanced Materials (18) 789-794), which is classified as amethanofullerene. Another methanofullerene derivative isThiophenyl-C₆₁-Butyric-Acid-Methyl-Ester ([60]ThCBM). Methanofullerenespossess many benefits compared to the native (un-derivatized) fullerenein organic electronics applications. One benefit is their increasedprocessability compared to native fullerenes, while maintaining much ofthe desirable electronic properties of the native fullerene. Theincrease in processability is due, in part, to an approximately ten-foldincrease in solubility in aromatic solvents. Non-methanofullerenederivatives include 2-Aza-Propano-(C_(n+2)N) fullerenes, also calledPrato adducts ([60]Prato).

[60]PCBM is typically blended with various conducting polymers which actas the electron donor and the [60]PCBM as the electron acceptor.Solution processing is used to form thin films comprising the electrondonor and electron acceptor. Although fullerene derivatives aretypically blended with various conducting polymers, it is possible toconstruct devices using only fullerene derivatives. Fullerenes andfullerene derivatives also have been shown to exhibit ambipolarelectronic behavior, transporting either holes or electrons, or both, inthe same device. Typical applications of [60]PCBM use [60]PCBM having apurity of about 99% or higher. Impurities in such compositions oftencomprise low amounts of pure C₆₀ fullerene, certain PCBM analogues ofC₆₀ fullerene, oxides of C₆₀ fullerene, oxides of PCBM, and traceamounts of other fullerenes. [60]PCBM is typically synthesized using C₆₀fullerene as the synthetic precursor where the purity of the C₆₀fullerene is typically about 99% or higher with respect to oxideimpurities, C₆₀-dimer, and small amounts of other fullerenes.

[70]PCBM is an analogue of [60]PCBM that can be prepared byderivatization of C₇₀ fullerene using a process analogous to that usedto prepare [60]PCBM from C₆₀ fullerene. [70]PCBM has been used as asemiconductor in organic electronics, particularly for polymer solardevices (Wienk et al., Angewadte Chemie, 2003, (115), 3493-3497) andtransistors (Anthopoulos et al., Journal of Applied Physics, (98),054503). Similar to [60]PCBM, [70]PCBM is typically used in purities ofapproximately 99%, though several isomers of [70]PCBM are present due tothe asymmetry of the C₇₀ and resulting difference in reactivity of thecarbons of the C₇₀ molecule. [70]PCBM is typically synthesized from C₇₀fullerene material having a purity of about 99%, and the impurities inC₇₀ fullerene are often similar to the impurities found in C₆₀. Incomparison to [60]PCBM, [70]PCBM is somewhat more soluble in organicsolvents, possibly due to the presence of multiple isomers. A relatedanalog, [84]PCBM, has also been synthesized and tested in organicphotodiodes and transistors.

Organic Electronic Devices

Organic electronic devices, such as bulk heterojunction photodiodes(Scharber et al., Advanced Materials (18) 789-794), are based on formingthin films (˜150 nm) of an electronic polymer and PCBM in the so-calleddonor/acceptor configuration where the polymer and PCBM phase-separateto form sub-micron size-scale domains with varying degrees of amorphousand crystalline structure. In the process of forming the heterojunctionthin film, the polymer and PCBM phase-separate and precipitate fromsolution upon drying and/or annealing of the film. Due to influences onelectron transport the size domains of the PCBM and degree ofcrystallinity have a strong impact on the resulting electronic behaviorand performance of the device. It has been shown through experimentaland theoretical analyses that the electron mobility (and resultingcurrent-carrying capacity, a strong determiner of the energy conversionefficiency) can be described with a Gaussian disorder model (Mihailetchiet al., Advanced Functional Materials, 2003, (13), 1.), which is knownalso to be the case for other materials, such as pure conductingpolymers. In this model, the degree of disorder (or lack ofcrystallinity) has a strong influence on the electron mobility which hasbeen seen with the drop in electron mobility of PCBM compared to singlecrystal C₆₀. Therefore, higher degrees of amorphous nature (i.e., lowercrystallinity) lead to reductions in electron mobility and correspondingreductions in energy conversion efficiency for organic electronicdevices. This effect can also be seen through the increase in energyconversion efficiency gained through annealing, which is known to givegreater crystallinity (less disorder or less amorphous nature) to thefilm (Ma et al., Advanced Functional Materials, 2005 (15), 1617-1622).

Virtually all organic electronic devices utilize a single n-typesemiconductor because certain impurities in the ppm level or even ppblevel can drastically alter device performance. For example, impuritiesin the ppm level or even ppb level can drastically alter deviceperformance for silicon-based electronics. The impact that impuritiescan have on device performance is linked in part to the disorderdescribed in preceding paragraph. However, impurities can alter theelectronics of the device for other reasons, including short-circuitingand electron trapping.

Various methanofullerene PCBM analogues have been made where solubilityis increased by the addition of C₄, C₈, C₁₂, or C₁₋₆ alkane units to theester of the PCBM (Zheng et al., Journal of Physical Chemistry B (108),32, 2004). Despite almost identical reduction potentials and UV/VISabsorption properties of the fullerene derivatives tested, the energyconversion efficiency is quite different for these different fullerenederivatives when used to fabricate organic solar cells with the samepolymer. This may be attributed to the different molecular interactionsbetween the polymer and fullerene derivative, which affect themorphology of the composition. The result may also be attributed todecreases in electron mobility brought about by the slight increase inthe different path-lengths to the C₆₀ fullerene core that functions asthe electron acceptor. The decrease in energy conversion efficiency from2.45 to 1.46 when PCB-C₈H₁₇ is used instead of PCB-C₄H₉ illustrates howthe energy conversion efficiency is sensitive to changes in thestructure of the fullerene derivative used as the n-type semiconductor.For the purposes of comparison, PCB-C₁₆H₃₃ gives an energy conversionefficiency of 0.11. This shows that such changes may occur solely inresponse to physical changes to the film brought about by changes in then-type semiconductor, even when n-type semiconductor compounds are usedthat are identical in reduction potential and light absorption spectrum.

Thin-film organic electronics device performance depends on a large setof processing and materials parameters, with a high degree of complexityin the interaction of these parameters to make up the final devicemorphological and electronics properties. It is often not possible topredict the effect that a change in the molecular structure of an n-typesemiconductor fullerene derivative will have on the final organicselectronics device performance, even knowing the reduction potential,absorption properties, and other electronic properties. This is mainlydue to the fact that the impact on the physical disorder of theresulting thin-film multi-phase system is difficult to predict a priori.Likewise, a change in type and level of impurities present in a givenfullerene derivative n-type semiconductor may affect the morphology andelectronics properties and resulting device performance of a thin-filmdevice in an unpredictable manner.

However, in view of the foregoing obstacles, new materials are neededfor thin-film organic electronic devices. The present invention fulfillsthis need and has other related advantages.

SUMMARY OF THE INVENTION

One aspect of the present invention relates to a composition comprisinga mixture of a C₆₀ fullerene derivative and a C₇₀ fullerene derivative.In certain instances, the ratio of the weight percentage of the C₆₀fullerene derivative to the C₇₀ fullerene derivative is about 2:1.

One aspect of the present invention relates to a composition comprisinga mixture of a C₆₀ methanofullerene and a C₇₀ methanofullerene. Incertain instances, the C₆₀ methanofullerene is aphenyl-butyric-acid-methyl-ester fullerene. In certain instances, theC₇₀ methanofullerene is a phenyl-butyric-acid-methyl-ester fullerene. Incertain instances, the ratio of the weight percentage of the C₆₀methanofullerene to C₇₀ methanofullerene is about 2:1. Another aspect ofthe present invention relates to a composition consisting essentially ofa mixture of a C₆₀ methanofullerene and a C₇₀ methanofullerene. Incertain instances, the C₆₀ methanofullerene is aphenyl-butyric-acid-methyl-ester fullerene. In certain instances, theC₇₀ methanofullerene is a phenyl-butyric-acid-methyl-ester fullerene.

Another aspect of the present invention relates to a compositioncomprising a mixture of a C₆₀ methanofullerene and a C₇₀methanofullerene. In certain instances, the C₆₀ methanofullerene is athiophenyl-butyric-acid-methyl-ester fullerene. In certain instances,the C₇₀ methanofullerene is a thiophenyl-butyric-acid-methyl-esterfullerene. In certain instances, the ratio of the weight percentage ofthe C₆₀ methanofullerene to C₇₀ methanofullerene is about 2:1. Anotheraspect of the present invention relates to a composition consistingessentially of a mixture of a C₆₀ methanofullerene and a C₇₀methanofullerene. In certain instances, the C₆₀ methanofullerene is athiophenyl-butyric-acid-methyl-ester fullerene. In certain instances,the C₇₀ methanofullerene is a thiophenyl-butyric-acid-methyl-esterfullerene.

Another aspect of the present invention relates to a compositioncomprising a mixture of a C₆₀ Prato adducts and C₇₀ Prato adducts. Incertain instances, the ratio of the weight percentage of [60]Pratofullerene to [70]Prato fullerene is about 2:1. Another aspect of thepresent invention relates to a composition consisting essentially of amixture of a [60]Prato fullerene and [70]Prato fullerene. In certaininstances, the [60]Prato fullerene is a 2-aza-propano-(C₆₂N) fullerene.In certain instances, the [70]Prato fullerene is a 2-aza-propano-(C₆₂N)fullerene.

Other aspects of the present invention relate to a compositioncomprising a mixture of [60] or [70] Bingel, diazoline, azafulleroid,ketolactam, or Diels Alder fullerene derivatives.

Another aspect of the present invention relates to methods of making andpurifying C₆₀ and C₇₀ fullerene derivatives. In certain instances, theC₆₀ or C₇₀ methanofullerene is a phenyl-butyric-acid-methyl-esterfullerene. In certain instances, the C₆₀ or C₇₀ methanofullerene is athiophenyl-butyric-acid-methyl-ester fullerene. In certain instances,the C₆₀ or C₇₀ fullerene is a Prato adduct.

Another aspect of the present invention relates to devices produced frommixtures of C₆₀ and C₇₀ fullerene derivatives. In certain instances, theC₆₀ or C₇₀ methanofullerene is a phenyl-butyric-acid-methyl-esterfullerene. In certain instances, the C₆₀ or C₇₀ methanofullerene is athiophenyl-butyric-acid-methyl-ester fullerene. In certain instances,the C₆₀ or C₇₀ fullerene is a Prato adduct.

Another aspect of the present invention relates to compositionscomprising mixtures of different C₆₀ and C₇₀ fullerene derivatives,e.g., blends of phenyl-butyric-acid-methyl-ester fullerenes withthiophenyl-butyric-acid-methyl-ester fullerenes or Prato adducts.

Another aspect of the present invention relates to compositionscomprising mixtures of C₆₀ and/or C₇₀ fullerene derivatives withnon-derivatized C₆₀ or C₇₀, e.g., blends of C₆₀ fullerene derivativesand C₇₀ fullerene derivatives with C₆₀ and/or C₇₀.

Another aspect of the present invention relates to compositionscomprising mixtures of mono-, bis-, and tris-adducts of C₆₀ and/or C₇₀fullerene derivatives.

Another aspect of the present invention relates to methods of producingand purifying mixtures of C60 fullerene derivatives and C70 fullerenederivatives, where the composition of the C60 derivative is about0.00001% to about 99.99999% and the composition of the C70 derivative isabout 0.00001% to about 99.99999%.

Another aspect of the present invention relates to semiconductorscomprised of mixtures of C60 fullerene derivatives and C70 fullerenederivatives.

Still another aspect of the present invention relates to devicescomprised of mixtures of C60 fullerene derivatives and C70 fullerenederivatives.

BRIEF DESCRIPTION OF FIGURES

FIG. 1 depicts energy conversion efficiency versus blend composition of[70]PCBM and [60]PCBM in a P3HT/PCBM bulk heterojunction solar celldevice. The weight % of [70]PCBM refers to the amount of [70]PCBMrelative to [60]PCBM (e.g., 100% refers to pure [70]PCBM 99% and no[60]PCBM). Impurities in the [70]PCBM are those typical for pure gradesof [70]PCBM (e.g., oxides and [70]PCBM analogues); the same is true forany impurities present in the [60]PCBM.

FIG. 2 Typical Bulk Heterojunction Photovoltaic Device Architecture.Bulk heterojunction refers to using a mixture of N-type and P-typesemiconductor. Acceptor refers to the N-type semiconductor which can bea composition claimed in this patent application. Donor refers to theP-type semiconductor, most commonly conjugated polymers such aspolythiophenes, for example poly-(3-hexylthiophene) (“P3HT”). The N-typeand P-type are dissolved typically in an aromatic solvent such aschlorobenzene, which is then typically deposited using solutionprocessing techniques, such as spin-coating or printing techniques, suchas ink jet printing. The unnamed layers are a transparent conductingoxide (TCO, e.g. ITO; top) and an ultra-thin protective layer (e.g. LiF;bottom).

DETAILED DESCRIPTION OF THE INVENTION

One aspect of the present invention provides compositions comprisingblends of C₆₀ fullerene derivatives and C₇₀ fullerene derivatives. Thecompositions are useful in a variety of applications, such asphotovoltaic cells, transistors, photodetectors, and sensors. In certaininstances, the C₆₀ fullerene derivatives and the C₇₀ fullerenederivatives are methanofullerene derivatives, such asphenyl-butyric-acid-methyl-ester fullerenes orthiophenyl-butyric-acid-methyl-ester fullerenes. In other instances, C₆₀fullerene derivatives and the C₇₀ fullerene derivatives are Pratoadducts. In still other instances, the blends are comprised of differentfullerene derivatives and/or a fullerene derivative and anon-derivatized fullerene. In certain instances, the blends of C₆₀fullerene derivatives and C₇₀ fullerene derivatives comprise mixturesmono-, bis-, and tris-adducts of fullerene derivatives.

Surprisingly, it has been found that blends of [60]PCBM and [70]PCBM,[60]ThCBM and [70]ThCBM, [60]Prato and [70]Prato, [60]ThCBM bis-adductsand [70]ThCBM bis-adducts, [60]PCBM and C₆₀, and [60]PCBM, [70]PCBM andC₆₀ show suitability as the semiconductor component in devices whereonly pure grades of either [60]PCBM or [70]PCBM have been used in thepast. The blends of C₆₀ and C₇₀ derivatives also show suitability over awide range of compositions for use as the semiconductor component. Theblends of C₆₀ and C₇₀ derivatives are particularly attractive becausethey are may be used with the same or similar processing conditions ofdevices optimized for either pure [60]PCBM or pure [70]PCBM. In fact,the results show that device performance, e.g., energy conversionefficiency for organic photovoltaic devices, shows very littlesensitivity to the blend composition, notwithstanding the fact that nomodification was made to the processing parameters, such as choice ofsolvent, evaporation time, processing temperature, etc. This result issurprising since such devices typically show a high degree ofsensitivity to processing conditions due to the phase-separation processand crystallization behavior of the PCBM, which causes changes inmorphology and level of disorder in the film affecting electronmobility. It is highly unusual that using two different fullerenederivatives with different physical properties (such as solubility andthe resultantly different crystallization behavior) prepared accordingto the same processing conditions gives nearly identical performance ofthe final device. Furthermore, we are unaware of any reported use of twoor more different n-type semiconductors concomitantly in the same devicein the field of organic electronics.

FIG. 1 shows the energy conversion efficiency of devices fabricatedunder identical processing conditions where the only difference was inthe composition of the n-type semiconductor. The n-type semiconductorwas made using a blend of [60]PCBM and [70]PCBM, each of which was 99%pure or higher with respect to compounds other than [60]PCBM and[70]PCBM. The weight percentage of [60]PCBM of the compositioncorresponding to a given weight % of [70]PCBM (as shown on the x-axis)was 99%-[weight % [70]PCBM]. Fullerenes higher in molecular weight thanC₇₀ and fullerene derivatives higher in molecular weight than [70]PCBMwere removed, since these compounds may act as electron traps anddiminish performance. In this example, the removal of these compoundswas performed after the PCBM synthesis, but it could also beadvantageous to remove all fullerenes higher in molecular weight thanC₇₀ from the fullerene mixture starting material before PCBM synthesisis carried out. The polymer used was poly-(3-hexylthiophene) (“P3HT”).The variation in the energy conversion efficiency across the variouscompositions in FIG. 1 was within the statistical variation of suchdevices, i.e., about 3% variation. Notably, such variations aretypically seen even when using entirely identical processing conditionswith the same batches of polymer and fullerene derivative. It can beappreciated that typical device non-uniformity is the substantial causeof the variation in energy conversion efficiency since the variation isscattered non-uniformly, as opposed to changing systematically withcomposition.

The results in FIG. 1 are especially surprising for the compositionswhere the weight % of [60]PCBM is equal to or higher than the weight %of [70]PCBM. The results are surprising because one might expect thatthe higher solubility of [70]PCBM, when combined with the lowerconcentrations relative to [60]PCBM, should lead to a significantlyreduced driving force for the onset and rate of crystallization causedby the lower levels of supersaturation. In particular, one might expect[60]PCBM-rich domains and [70]PCBM-rich domains to give differences inthe morphology and electronic behavior of the film because the rates ofcrystallization of the PCBM mixture components would be expected to bedifferent from either pure [70]PCBM or [60]PCBM alone. In fact, it isgenerally recognized that significant optimization efforts are requiredto obtain the highest energy conversion efficiency of a given devicesystem when different polymers, fullerene derivatives, or even thepolymer molecular weight and regioregularity or purities of thefullerene derivative are used. Optimization efforts are often requiredbecause small changes in processing conditions and materials can causesignificant changes in device performance. The changes in deviceperformance can be attributed to film morphology changes. Notably, smalldifferences in the average domain size of PCBM or polymer can causesignificant changes in overall performance of the device. The effect ofsuch differences is magnified by the fact that the overall filmthickness is often only approximately 150 nm.

The result that blends of [60]PCBM and [70]PCBM show suitability as thesemiconductor component in devices is also surprising in view the factthat the electronic properties of thin-films of polymer/[60]PCBM andpolymer/[70]PCBM are significantly different. For example, it has alsobeen shown that the open-circuit voltage and fill factor of pure[70]PCBM/MDMO-PPV devices is significantly lower than in[60]PCBM/MDMO-PPV devices (Wienk et al., Angewadte Chemie, 2003, (115),3493-3497). Accordingly, the fact that blends of blends of [60]PCBM and[70]PCBM can be used without any noticeable effect on the electronicdevice performance, and most importantly under identical processingconditions, is surprising.

The use of a mixture of a C₆₀ fullerene derivative and a C₇₀ fullerenederivative in a semiconductor composition in electronics devices isadvantageous because it is much less expensive to prepare a mixture of aC₆₀ fullerene derivative and a C₇₀ fullerene derivative compared to apure C₆₀ or C₇₀ fullerene derivative. Preparation of a pure C₆₀ or C₇₀fullerene derivative necessarily requires expensive purificationprocesses at some stage in the synthesis in order to separatenon-isomeric fullerenes. The purification is necessary because knownprocesses for producing native fullerene feedstocks, such as arcvaporization, laser ablation, combustion, etc. produce mixtures offullerenes. For example, C₆₀ is typically produced in the highestproportion, while C₇₀, C₈₄, and C_(76/)C₇₈, are produced in decreasingamounts. Typical product compositions of fullerenes produced by the arcvaporization process are approximately 65% C60, 30% C70, and 5%fullerenes higher in molecular weight than C₇₀. Combustion synthesis canproduce nearly equal amounts of C₇₀ and C₆₀, and even more C₇₀ than C₆₀in certain instances.

The fullerenes produced from a fullerene production process are purifiedinto the individual fullerene species by purification processes, whichtypically require solvent processing, but in all cases lead to addedexpense because the purification step is in addition to the fullereneproduction step. Solvent processing often requires a large amount ofsolvent and a relatively long time for purification since the solubilityof fullerenes is relatively low. Consequently, pure fullerenes aresignificantly more expensive than fullerene mixtures. For example,fullerene extract (where only the amorphous carbon and/or othernon-fullerene material has been removed) costs at current market ratesapproximately $6/g at kilogram scale and 99% C₆₀ costs approximately$20/g. Therefore, the cost of the native fullerene starting material isa significant component of the final cost associated with production ofPCBM fullerenes.

It is also noteworthy that the devices compared in FIG. 1 give astate-of-the-art energy conversion efficiency since the processingconditions were optimized for the pure [60]PCBM. The apparent lack of adependency of energy conversion efficiency on the n-type semiconductorcompositions tested occurs at already optimized processing conditions.This allows for the blend compositions potentially to be used to replacethe typical pure PCBM semiconductors with minimal work required tore-optimize a given system. The fact that the C60/C70 fullerene blendsof the invention should be compatible with devices currently using puregrades of PCBM is significant because essentially all known deviceswhich use PCBM are based on pure grades of PCBM. The cost savingsassociated with preparing mixtures of [60]PCBM and [70]PCBM also appliesto other compositions, such as a ‘higher fullerene” mixture comprisingC₇₆/C₇₈/C₈₄, which is less expensive than C₈₄.

It is also envisioned that blends of [60]PCBM and [70]PCBM may offerenhanced energy conversion efficiency in certain systems as compared tothe typically-used pure [70]PCBM. See Wienk et al., Angewandte Chemie,2003, (115), 3493-3497). For example, a 90% [70]PCBM grade, where theremaining components were 9% [60]PCBM and 1% typical PCBM impurities,gave identical device performance in a poly(2-methoxy,5-(2′-ethyl-hexyloxy)-p-phenylene vinylene) (MEH-PPV)/PCBM solar cellcompared to [70]PCBM 99%. Notably, the pure [70]PCBM 99% device wassignificantly higher in energy conversion efficiency than the samedevice configuration with [60]PCBM. The 90% [70]PCBM also gave identicalresults to the PCBM 99% with no change in processing conditions.

Table 1 shows the energy conversion efficiency of a variety mixtures ofC₆₀ and C₇₀ derivatives, with and without underivatized C₆₀,demonstrating the general applicability of this invention to mixtures offullerene derivatives.

TABLE 1 Power Conversion Efficiency for P3HT/N-type (1:1) bulkheterojunction photovoltaic cells solution processed using chlorobenzeneas solvent. Composition percentages of fullerene mixtures are determinedby HPLC at a wavelength of 360 nm, on an analytical Cosmosil Buckyprepcolumn (4.6 × 250 mm), with the assumption that all fullerenes andfullerene derivatives have equal molar extinction coefficients at 360nm. Power Conversion N-type Compound Efficiency (%) [60]PCBM 3.5[70]PCBM 3.5 [60]PCBM:[70]PCBM (3:1) 3.9 >[70]PCBM's (4% molar) 0.1[60]ThCBM 4.1 [70]ThCBM 4.3 [60]ThCBM:[70]ThCBM (3:1) 4.1 >[70]ThCBM's(4% molar) 0.2 [60]Prato/[70]Prato (1.5:1) 1.5 [60]Prato/[70]Prato (4:1)0.6 [60]ThCBM bis-adducts 2.9 [70]ThCBM bis-adducts 2.5[60]ThCBM:[70]ThCBM (3:1) bis-adducts 2.7 [60]PCBM 3.5 [60]PCBM + C60(2.5% molar) 3.5 [60]PCBM:[70]PCBM (3:1) 3.0 [60]PCBM:[70]PCBM (3:1) +C₆₀ (13% 2.6 molar) [60]PCBM:[70]PCBM (3:1) + C₆₀ (39% 2.2 molar)

In Table 1, “>70[PCBM's” describes PCBM derivatives greater than C₇₀.These molecules act as electron traps and degrade device performance.These results demonstrate that one can use mixtures of C₆₀ and C₇₀derivatives, where the derivatives can be any methanofullerene or Pratoadduct, as an N-type in an organic photovoltaic device. Surprisingly,the data indicate that inclusion of C₆₀ up to 39% molar (and byextension pure C70) does not completely degrade device performance.

Uses

The mixed compositions of C₆₀ and C₇₀ derivatives described herein maybe used as semiconductor compounds, either n-type or ambipolar (capableof both n-type and p-type semiconducting), either alone or inconjunction with one or more electronic polymers, such as conjugatedpolymers, or pure C₆₀ or C₇₀. The mixed compositions of C₆₀ and C₇₀derivatives described here may be used in conjunction with conjugatedpolymers to form donor/acceptor systems, including thin-film deviceswhere the conjugated polymer may be any polymer that gives suitabledonor properties, such as, but not limited to: p-type oligomers andpolymers of derivatized and underivatized thiophenes, phenylenes,fluorenes, acetylenes, isothionaphthenes, benzthiaziazoles, pyrroles andcombinations thereof. In some embodiments, the polymer is selected fromthe group of (phenylene vinylene) oligomers and polymers, such aspoly[(2-methoxy-5-(3′,7′,-dimethyloctyloxy)]-p-phenylene vinylene(MDMO-PPV) or selected from oligomer or polymer thiophenes, such aspoly-(3-hexylthiophene) (“P3HT”).

In instances relating to the use in thin-film devices, the mixedcompositions of C₆₀ and C₇₀ derivatives described herein may be used asthe n-type semiconductor either mixed with the p-type semiconductor(e.g., a conjugated polymer), or the p-type and n-type semiconductorsmay be in separate layers of the device. When the mixture of C₆₀ and C₇₀derivatives described herein is mixed with a p-type conjugated polymerto form bulk heterojunction devices, blends, or copolymers, the weightto weight ratio of p-type material to fullerene can be in the range of10:1 wt % to 1:10 wt %; 1:1 wt % to 1:5 wt %; or 1:2 wt % to 1:4 wt %.

Devices

Any suitable device architecture known in the art based on pure gradesof fullerene derivatives may be used to construct the organic electronicdevices described herein by simply replacing the pure grades of PCBMwith the mixed compositions of C₆₀ and C₇₀ derivatives described herein.In some embodiments, PCBM, ThCBM, or Prato n-type semiconductors areused. In some cases, no particular optimization may be required due tosubstituting the pure grade of PCBM with the mixed compositions of C₆₀and C₇₀ derivatives. However, certain cases may require routineoptimization in order to obtain the best device performance.

Methanofullerenes

One example of a fullerene derivative of the invention is amethanofullerene having the general structure:

The —C(X)(Y)— group is bonded to the fullerene via a methano-bridge, asobtained through the well-known diazoalkane addition chemistry (W.Andreoni (ed.), The chemical Physics of Fullerenes 10 (and 5) YearsLater, 257-265, Kluwer, 1996.) and X and Y are aryl, alkyl, or otherchemical moieties which can be suitably bonded via the diazoalkaneaddition either by modification of the diazoalkane precursor or afterthe diazoalkane addition by modification of the fullerene derivative.Most common is the molecule where X is an unsubstituted aryl, and Y isButyric-Acid-Methyl-Ester, which molecule is commonly termed PCBM. Inthe mono-adduct derivative n is 1; in the bis-adduct derivative, n is 2,and so on.

Blends of C₆₀ and C₇₀ methanofullerene derivatives can be prepared byderivatizing a mixture of unmodified C₆₀ and C₇₀ fullerenes. Forexample, a mixture of [60]PCBM/[70]PCBM can be prepared by subjecting amixture of unmodified C₆₀ and C₇₀ fullerenes to the conditions describedin Hummelen et al. J. Org. Chem. 1995, 60, 532 or US2005/0239717 for thepreparation of [60]PCBM, [70]PCBM, and [84]PCBM. Both Hummelen et al.and US2005/0239717 are hereby incorporated by reference. The ratio of[60]PCBM to [70]PCBM in the final mixture can be varied by adjusting theratio of C₆₀ fullerene to C₇₀ fullerene in the starting material usedfor the derivatization reaction. Alternatively, the ratio of [60]PCBM to[70]PCBM in the final mixture can be adjusted by subjecting the mixtureof [60]PCBM and [70]PCBM to various analytical techniques known in theart.

A photodiode comprising the fullerene blends of the invention may beprepared following procedures known in the art for constructing aphotodiode, wherein the fullerene blend of the invention is substitutedfor the pure fullerene derivative used in the known procedures. Forexample, a mixture of [60]PCBM and [70]PCBM may be used in place of thepure [70]PCBM described in WO04/073082 for the preparation of a solarcell. WO04/073082 is hereby incorporated by reference.

Prato Fullerene Derivatives

A Prato fullerene derivative is represented by:

wherein

A is a fullerene bonded to —C(R₄R₅)—N(R₃)—C(R₁R₂)—;

R₁ is optionally substituted aryl or aralkyl;

R₂, R₃, R₄, and R₅ are independently optionally substituted alkyl,optionally substituted cycloalkyl, optionally substituted heteroalkyl,optionally substituted heterocycloalkyl, optionally substituted alkenyl,or optionally substituted aralkyl; and

-   -   n is 1 to 40.        Other Fullerene Derivatives

The compositions, devices, and methods disclosed herein are applicableto any type of chemical derivative of fullerenes, such as those above,but not limited to the derivative types mentioned above.

Bingel Derivatives

The structure of a Bingel derivative is represented by:

wherein

z is 1 to 40;

X is an electron withdrawing group (EWG) such as ester, nitrile, nitro,cyano, ketone, dialkylphosphate, (substituted) pyridine, C-(triplebond)-C—R, (a.k.a. an acetylene) and R is Si—(R)3, or a trisubstitutedsilyl group (same or different); and

Y is H, aryl, substituted aryl, alkyl, substituted alkyl.

Diazoline Derivatives

The structure of a Diazoline derivative is represented by:

wherein

R and R′ are independently aryls; and

x is 1 to 40.

Azafulleroid Derivatives

The structure of an Azafulleroid derivative is represented by:

wherein

x is 1 to 40; and

R is alkyl, substituted alkyl, aryl, substituted aryl, SO₂—R′, whereinR′ is alkyl, aryl, substituted aryl.

Ketolactam Derivatives

The structure of a Ketolactam Adduct is represented by:

wherein

R is an alkyl or a substituted alkyl; and

n is 1 to 40.

Diels Alder Derivatives

The structure of a Diels Alder derivative is represented by:

wherein

x is 1 to 40;

Cn is a fullerene;

R₁ is H, alkyl, alkyloxy, aryl, substituted alkyl, substituted aryl,heteroaryl, or substituted heteroaryl;

R₂ is H, alkyl, alkyloxy, aryl, substituted alkyl, substituted aryl,heteroaryl, or substituted heteroaryl;

X is O, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, orsubstituted heteroaryl;

Y is aryl, substituted aryl, heteroaryl, substituted heteroaryl,vinylene, or substituted vinylene;

Or a compound with the general structure

wherein

x is 1 to 40;

Cn is a fullerene;

R₁ is H, alkyl, alkyloxy, aryl, substituted alkyl, substituted aryl,heteroaryl, or substituted heteroaryl;

R₂ is H, alkyl, alkyloxy, aryl, substituted alkyl, substituted aryl,heteroaryl, or substituted heteroaryl;

Y is aryl, substituted aryl, heteroaryl, substituted heteroaryl,vinylene, or substituted vinylene.

Mixtures of C₆₀ and C₇₀ Fullerenes Derivatized with the Same Entity

The compositions described herein may comprise mixtures of C₆₀ and C₇₀fullerenes each derivatized with PCBM, including: mixtures of about 95%[60]PCBM and about 5% [70]PCBM, mixtures of about 85% [60]PCBM and about15% [70]PCBM, mixtures of about 75% [60]PCBM and about 25% [70]PCBM,mixtures of about 65% [60]PCBM and about 35% [70]PCBM, mixtures of about55% [60]PCBM and about 45% [70]PCBM, mixtures of about 45% [60]PCBM andabout 55% [70]PCBM, mixtures of about 35% [60]PCBM and about 65%[70]PCBM, mixtures of about 25% [60]PCBM and about 75% [70]PCBM,mixtures of about 15% [60]PCBM and about 85% [70]PCBM, and mixtures ofabout 5% [60]PCBM and about 95% [70]PCBM.

The compositions described herein may comprise mixtures of C₆₀ and C₇₀fullerenes each derivatized with ThCBM, including: mixtures of about 95%[60]ThCBM and about 5% [70]ThCBM, mixtures of about 85% [60]ThCBM andabout 15% [70]ThCBM, mixtures of about 75% [60]ThCBM and about 25%[70]ThCBM, mixtures of about 65% [60]ThCBM and about 35% [70]ThCBM,mixtures of about 55% [60]ThCBM and about 45% [70]ThCBM, mixtures ofabout 45% [60]ThCBM and about 55% [70]ThCBM, mixtures of about 35%[60]ThCBM and about 65% [70]ThCBM, mixtures of about 25% [60]ThCBM andabout 75% [70]ThCBM, mixtures of about 15% [60]ThCBM and about 85%[70]ThCBM, and mixtures of about 5% [60]ThCBM and about 95% [70]ThCBM.

The compositions described herein may comprise mixtures of C₆₀ and C₇₀fullerenes each derivatized with Prato adducts, including: mixtures ofabout 95% [60]Prato and about 5% [70]Prato, mixtures of about 85%[60]Prato and about 15% [70]Prato, mixtures of about 75% [60]Prato andabout 25% [70]Prato, mixtures of about 65% [60]Prato and about 35%[70]Prato, mixtures of about 55% [60]Prato and about 45% [70]Prato,mixtures of about 45% [60]Prato and about 55% [70]Prato, mixtures ofabout 35% [60]Prato and about 65% [70]Prato, mixtures of about 25%[60]Prato and about 75% [70]Prato, mixtures of about 15% [60]Prato andabout 85% [70]Prato, and mixtures of about 5% [60]Prato and about 95%[70]Prato.

Mixtures of C₆₀ and C₇₀ Fullerenes Derivatized with Different Entities

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with PCBM and C₇₀ fullerenes derivatized withThCBM, including: mixtures of about 95% [60]PCBM and about 5% [70]ThCBM,mixtures of about 85% [60]PCBM and about 15% [70]ThCBM, mixtures ofabout 75% [60]PCBM and about 25% [70]ThCBM, mixtures of about 65%[60]PCBM and about 35% [70]ThCBM, mixtures of about 55% [60]PCBM andabout 45% [70]ThCBM, mixtures of about 45% [60]PCBM and about 55%[70]ThCBM, mixtures of about 35% [60]PCBM and about 65% [70]ThCBM,mixtures of about 25% [60]PCBM and about 75% [70]ThCBM, mixtures ofabout 15% [60]PCBM and about 85% [70]ThCBM, and mixtures of about 5%[60]PCBM and about 95% [70]ThCBM.

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with PCBM and C₇₀ fullerenes derivatized withPrato adducts, including: mixtures of about 95% [60]PCBM and about 5%[70]Prato, mixtures of about 85% [60]PCBM and about 15% [70]Prato,mixtures of about 75% [60]PCBM and about 25% [70]Prato, mixtures ofabout 65% [60]PCBM and about 35% [70]Prato, mixtures of about 55%[60]PCBM and about 45% [70]Prato, mixtures of about 45% [60]PCBM andabout 55% [70]Prato, mixtures of about 35% [60]PCBM and about 65%[70]Prato, mixtures of about 25% [60]PCBM and about 75% [70]Prato,mixtures of about 15% [60]PCBM and about 85% [70]Prato, and mixtures ofabout 5% [60]PCBM and about 95% [70]Prato.

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with ThCBM and C₇₀ fullerenes derivatized withPCBM, including: mixtures of about 95% [60]ThCBM and about 5% [70]PCBM,mixtures of about 85% [60]ThCBM and about 15% [70]PCBM, mixtures ofabout 75% [60]ThCBM and about 25% [70]PCBM, mixtures of about 65%[60]ThCBM and about 35% [70]PCBM, mixtures of about 55% [60]ThCBM andabout 45% [70]PCBM, mixtures of about 45% [60]ThCBM and about 55%[70]PCBM, mixtures of about 35% [60]ThCBM and about 65% [70]PCBM,mixtures of about 25% [60]ThCBM and about 75% [70]PCBM, mixtures ofabout 15% [60]ThCBM and about 85% [70]PCBM, and mixtures of about 5%[60]ThCBM and about 95% [70]PCBM.

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with ThCBM and C₇₀ fullerenes derivatized withPrato adducts, including: mixtures of about 95% [60]ThCBM and about 5%[70]Prato, mixtures of about 85% [60]ThCBM and about 15% [70]Prato,mixtures of about 75% [60]ThCBM and about 25% [70]Prato, mixtures ofabout 65% [60]ThCBM and about 35% [70]Prato, mixtures of about 55%[60]ThCBM and about 45% [70]Prato, mixtures of about 45% [60]ThCBM andabout 55% [70]Prato, mixtures of about 35% [60]ThCBM and about 65%[70]Prato, mixtures of about 25% [60]ThCBM and about 75% [70]Prato,mixtures of about 15% [60]ThCBM and about 85% [70]Prato, and mixtures ofabout 5% [60]ThCBM and about 95% [70]Prato.

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with Prato adducts and C₇₀ fullerenes derivatizedwith PCBM, including: mixtures of about 95% [60]Prato and about 5%[70]PCBM, mixtures of about 85% [60]Prato and about 15% [70]PCBM,mixtures of about 75% [60]Prato and about 25% [70]PCBM, mixtures ofabout 65% [60]Prato and about 35% [70]PCBM, mixtures of about 55%[60]Prato and about 45% [70]PCBM, mixtures of about 45% [60]Prato andabout 55% [70]PCBM, mixtures of about 35% [60]Prato and about 65%[70]PCBM, mixtures of about 25% [60]Prato and about 75% [70]PCBM,mixtures of about 15% [60]Prato and about 85% [70]PCBM, and mixtures ofabout 5% [60]Prato and about 95% [70]PCBM.

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with Prato adducts and C₇₀ fullerenes derivatizedwith ThCBM, including: mixtures of about 95% [60]Prato and about 5%[70]ThCBM, mixtures of about 85% [60]Prato and about 15% [70]ThCBM,mixtures of about 75% [60]Prato and about 25% [70]ThCBM, mixtures ofabout 65% [60]Prato and about 35% [70]ThCBM, mixtures of about 55%[60]Prato and about 45% [70]ThCBM, mixtures of about 45% [60]Prato andabout 55% [70]ThCBM, mixtures of about 35% [60]Prato and about 65%[70]ThCBM, mixtures of about 25% [60]Prato and about 75% [70]ThCBM,mixtures of about 15% [60]Prato and about 85% [70]ThCBM, and mixtures ofabout 5% [60]Prato and about 95% [70]ThCBM.

Mixtures of Derivatized and Unreacted C60 Fullerenes

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with PCBM and unreacted C₆₀ fullerenes,including: mixtures of about 97% [60]PCBM and about 3% [60], about 87%[60]PCBM and about 13% [60], about 77% [60]PCBM and about 23% [60],about 67% [60]PCBM and about 33% [60], about 57% [60]PCBM and about 43%[60], about 47% [60]PCBM and about 53% [60], about 37% [60]PCBM andabout 63% [60], about 27% [60]PCBM and about 73% [60], about 17%[60]PCBM and about 83% [60], and about 7% [60]PCBM and about 93% [60].

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with ThCBM and unreacted C₆₀ fullerenes,including: mixtures of about 97% [60]ThCBM and about 3% [60], about 87%[60]ThCBM and about 13% [60], about 77% [60]ThCBM and about 23% [60],about 67% [60]ThCBM and about 33% [60], about 57% [60]ThCBM and about43% [60], about 47% [60]ThCBM and about 53% [60], about 37% [60]ThCBMand about 63% [60], about 27% [60]ThCBM and about 73% [60], about 17%[60]ThCBM and about 83% [60], and about 7% [60]ThCBM and about 93% [60].

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with Prato adducts and unreacted C₆₀ fullerenes,including: mixtures of about 97% [60]Prato and about 3% [60], about 87%[60]Prato and about 13% [60], about 77% [60]Prato and about 23% [60],about 67% [60]Prato and about 33% [60], about 57% [60]Prato and about43% [60], about 47% [60]Prato and about 53% [60], about 37% [60]Pratoand about 63% [60], about 27% [60]Prato and about 73% [60], about 17%[60]Prato and about 83% [60], and about 7% [60]Prato and about 93% [60].

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with Bingel and unreacted C₆₀ fullerenes,including: mixtures of about 97% [60]Bingel and about 3% [60], about 87%[60]Bingel and about 13% [60], about 77% [60]Bingel and about 23% [60],about 67% [60]Bingel and about 33% [60], about 57% [60]Bingel and about43% [60], about 47% [60]Bingel and about 53% [60], about 37% [60]Bingeland about 63% [60], about 27% [60]Bingel and about 73% [60], about 17%[60]Bingel and about 83% [60], and about 7% [60]Bingel and about 93%[60].

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with diazoline and unreacted C₆₀ fullerenes,including: mixtures of about 97% [60]diazoline and about 3% [60], about87% [60]diazoline and about 13% [60], about 77% [60]diazoline and about23% [60], about 67% [60]diazoline and about 33% [60], about 57%[60]diazoline and about 43% [60], about 47% [60]diazoline and about 53%[60], about 37% [60]diazoline and about 63% [60], about 27%[60]diazoline and about 73% [60], about 17% [60]diazoline and about 83%[60], and about 7% [60]diazoline and about 93% [60].

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with azafulleroid and unreacted C₆₀ fullerenes,including: mixtures of about 97% [60]azafulleroid and about 3% [60],about 87% [60]azafulleroid and about 13% [60], about 77%[60]azafulleroid and about 23% [60], about 67% [60]azafulleroid andabout 33% [60], about 57% [60]azafulleroid and about 43% [60], about 47%[60]azafulleroid and about 53% [60], about 37% [60]azafulleroid andabout 63% [60], about 27% [60]azafulleroid and about 73% [60], about 17%[60]azafulleroid and about 83% [60], and about 7% [60]azafulleroid andabout 93% [60].

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with ketolactam and unreacted C₆₀ fullerenes,including: mixtures of about 97% [60]ketolactam and about 3% [60], about87% [60]ketolactam and about 13% [60], about 77% [60]ketolactam andabout 23% [60], about 67% [60]ketolactam and about 33% [60], about 57%[60]ketolactam and about 43% [60], about 47% [60]ketolactam and about53% [60], about 37% [60]ketolactam and about 63% [60], about 27%[60]ketolactam and about 73% [60], about 17% [60]ketolactam and about83% [60], and about 7% [60]ketolactam and about 93% [60].

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with Diels Alder and unreacted C₆₀ fullerenes,including: mixtures of about 97% [60]Diels Alder and about 3% [60],about 87% [60]Diels Alder and about 13% [60], about 77% [60]Diels Alderand about 23% [60], about 67% [60]Diels Alder and about 33% [60], about57% [60]Diels Alder and about 43% [60], about 47% [60]Diels Alder andabout 53% [60], about 37% [60]Diels Alder and about 63% [60], about 27%[60]Diels Alder and about 73% [60], about 17% [60]Diels Alder and about83% [60], and about 7% [60]Diels Alder and about 93% [60].

Mixtures of Derivatized and Unreacted C70 Fullerenes

The compositions described herein may comprise mixtures of C70fullerenes derivatized with PCBM and unreacted C₆₀ fullerenes,including: mixtures of about 97% [70]PCBM and about 3% [70], about 87%[70]PCBM and about 13% [70], about 77% [70]PCBM and about 23% [70],about 67% [70]PCBM and about 33% [70], about 57% [70]PCBM and about 43%[70], about 47% [70]PCBM and about 53% [70], about 37% [70]PCBM andabout 63% [70], about 27% [70]PCBM and about 73% [70], about 17%[70]PCBM and about 83% [70], and about 7% [70]PCBM and about 93% [70].

The compositions described herein may comprise mixtures of C₇₀fullerenes derivatized with ThCBM and unreacted C₆₀ fullerenes,including: mixtures of about 97% [70]ThCBM and about 3% [70], about 87%[70]ThCBM and about 13% [70], about 77% [70]ThCBM and about 23% [70],about 67% [70]ThCBM and about 33% [70], about 57% [70]ThCBM and about43% [70], about 47% [70]ThCBM and about 53% [70], about 37% [70]ThCBMand about 63% [70], about 27% [70]ThCBM and about 73% [70], about 17%[70]ThCBM and about 83% [70], and about 7% [70]ThCBM and about 93% [70].

The compositions described herein may comprise mixtures of C₇₀fullerenes derivatized with Prato adducts and unreacted C₆₀ fullerenes,including: mixtures of about 97% [70]Prato and about 3% [70], about 87%[70]Prato and about 13% [70], about 77% [70]Prato and about 23% [70],about 67% [70]Prato and about 33% [70], about 57% [70]Prato and about43% [70], about 47% [70]Prato and about 53% [70], about 37% [70]Pratoand about 63% [70], about 27% [70]Prato and about 73% [70], about 17%[70]Prato and about 83% [70], and about 7% [70]Prato and about 93% [70].

The compositions described herein may comprise mixtures of C₇₀fullerenes derivatized with Bingel and unreacted C₇₀ fullerenes,including: mixtures of about 97% [70]Bingel and about 3% [70], about 87%[70]Bingel and about 13% [70], about 77% [70]Bingel and about 23% [70],about 67% [70]Bingel and about 33% [70], about 57% [70]Bingel and about43% [70], about 47% [70]Bingel and about 53% [70], about 37% [70]Bingeland about 63% [70], about 27% [70]Bingel and about 73% [70], about 17%[70]Bingel and about 83% [70], and about 7% [70]Bingel and about 93%[70].

The compositions described herein may comprise mixtures of C₇₀fullerenes derivatized with diazoline and unreacted C₇₀ fullerenes,including: mixtures of about 97% [70]diazoline and about 3% [70], about87% [70]diazoline and about 13% [70], about 77% [70]diazoline and about23% [70], about 67% [70]diazoline and about 33% [70], about 57%[70]diazoline and about 43% [70], about 47% [70]diazoline and about 53%[70], about 37% [70]diazoline and about 63% [70], about 27%[70]diazoline and about 73% [70], about 17% [70]diazoline and about 83%[70], and about 7% [70]diazoline and about 93% [70].

The compositions described herein may comprise mixtures of C₇₀fullerenes derivatized with azafulleroid and unreacted C₇₀ fullerenes,including: mixtures of about 97% [70]azafulleroid and about 3% [70],about 87% [70]azafulleroid and about 13% [70], about 77%[70]azafulleroid and about 23% [70], about 67% [70]azafulleroid andabout 33% [70], about 57% [70]azafulleroid and about 43% [70], about 47%[70]azafulleroid and about 53% [70], about 37% [70]azafulleroid andabout 63% [70], about 27% [70]azafulleroid and about 73% [70], about 17%[70]azafulleroid and about 83% [70], and about 7% [70]azafulleroid andabout 93% [70].

The compositions described herein may comprise mixtures of C₇₀fullerenes derivatized with ketolactam and unreacted C₇₀ fullerenes,including: mixtures of about 97% [70]ketolactam and about 3% [70], about87% [70]ketolactam and about 13% [70], about 77% [70]ketolactam andabout 23% [70], about 67% [70]ketolactam and about 33% [70], about 57%[70]ketolactam and about 43% [70], about 47% [70]ketolactam and about53% [70], about 37% [70]ketolactam and about 63% [70], about 27%[70]ketolactam and about 73% [70], about 17% [70]ketolactam and about83% [70], and about 7% [70]ketolactam and about 93% [70].

The compositions described herein may comprise mixtures of C₇₀fullerenes derivatized with Diels Alder and unreacted C₇₀ fullerenes,including: mixtures of about 97% [70]Diels Alder and about 3% [70],about 87% [70]Diels Alder and about 13% [70], about 77% [70]Diels Alderand about 23% [70], about 67% [70]Diels Alder and about 33% [70], about57% [70]Diels Alder and about 43% [70], about 47% [70]Diels Alder andabout 53% [70], about 37% [70]Diels Alder and about 63% [70], about 27%[70]Diels Alder and about 73% [70], about 17% [70]Diels Alder and about83% [70], and about 7% [70]Diels Alder and about 93% [70].

Mixtures of C₆₀ and C₇₀ Fullerene Bis-Derivatives, Derivatized with theSame Entity

The compositions described herein may comprise mixtures of C₆₀ and C₇₀fullerenes each derivatized with PCBM, including: mixtures of about 95%[60]-bis-PCBM and about 5% [70]-bis-PCBM, mixtures of about 85%[60]-bis-PCBM and about 15% [70]-bis-PCBM, mixtures of about 75%[60]-bis-PCBM and about 25% [70]-bis-PCBM, mixtures of about 65%[60]-bis-PCBM and about 35% [70]-bis-PCBM, mixtures of about 55%[60]-bis-PCBM and about 45% [70]-bis-PCBM, mixtures of about 45%[60]-bis-PCBM and about 55% [70]-bis-PCBM, mixtures of about 35%[60]-bis-PCBM and about 65% [70]-bis-PCBM, mixtures of about 25%[60]-bis-PCBM and about 75% [70]-bis-PCBM, mixtures of about 15%[60]-bis-PCBM and about 85% [70]-bis-PCBM, and mixtures of about 5%[60]-bis-PCBM and about 95% [70]-bis-PCBM.

The compositions described herein may comprise mixtures of C₆₀ and C₇₀fullerenes each derivatized with ThCBM, including: mixtures of about 95%[60]-bis-ThCBM and about 5% [70]-bis-ThCBM, mixtures of about 85%[60]-bis-ThCBM and about 15% [70]-bis-ThCBM, mixtures of about 75%[60]-bis-ThCBM and about 25% [70]-bis-ThCBM, mixtures of about 65%[60]-bis-ThCBM and about 35% [70]-bis-ThCBM, mixtures of about 55%[60]-bis-ThCBM and about 45% [70]-bis-ThCBM, mixtures of about 45%[60]-bis-ThCBM and about 55% [70]-bis-ThCBM, mixtures of about 35%[60]-bis-ThCBM and about 65% [70]-bis-ThCBM, mixtures of about 25%[60]-bis-ThCBM and about 75% [70]-bis-ThCBM, mixtures of about 15%[60]-bis-ThCBM and about 85% [70]-bis-ThCBM, and mixtures of about 5%[60]-bis-ThCBM and about 95% [70]-bis-ThCBM.

The compositions described herein may comprise mixtures of C₆₀ and C₇₀fullerenes each derivatized with Prato adducts, including: mixtures ofabout 95% [60]-bis-Prato and about 5% [70]-bis-Prato, mixtures of about85% [60]-bis-Prato and about 15% [70]-bis-Prato, mixtures of about 75%[60]-bis-Prato and about 25% [70]-bis-Prato, mixtures of about 65%[60]-bis-Prato and about 35% [70]-bis-Prato, mixtures of about 55%[60]-bis-Prato and about 45% [70]-bis-Prato, mixtures of about 45%[60]-bis-Prato and about 55% [70]-bis-Prato, mixtures of about 35%[60]-bis-Prato and about 65% [70]-bis-Prato, mixtures of about 25%[60]-bis-Prato and about 75% [70]-bis-Prato, mixtures of about 15%[60]-bis-Prato and about 85% [70]-bis-Prato, and mixtures of about 5%[60]-bis-Prato and about 95% [70]-bis-Prato.

The compositions described herein may comprise mixtures of C₆₀ and C₇₀fullerenes each derivatized with Bingel, including: mixtures of about95% [60]-bis-Bingel and about 5% [70]-bis-Bingel, mixtures of about 85%[60]-bis-Bingel and about 15% [70]-bis-Bingel, mixtures of about 75%[60]-bis-Bingel and about 25% [70]-bis-Bingel, mixtures of about 65%[60]-bis-Bingel and about 35% [70]-bis-Bingel, mixtures of about 55%[60]-bis-Bingel and about 45% [70]-bis-Bingel, mixtures of about 45%[60]-bis-Bingel and about 55% [70]-bis-Bingel, mixtures of about 35%[60]-bis-Bingel and about 65% [70]-bis-Bingel, mixtures of about 25%[60]-bis-Bingel and about 75% [70]-bis-Bingel, mixtures of about 15%[60]-bis-Bingel and about 85% [70]-bis-Bingel, and mixtures of about 5%[60]-bis-Bingel and about 95% [70]-bis-Bingel.

The compositions described herein may comprise mixtures of C₆₀ and C₇₀fullerenes each derivatized with diazoline, including: mixtures of about95% [60]-bis-diazoline and about 5% [70]-bis-diazoline, mixtures ofabout 85% [60]-bis-diazoline and about 15% [70]-bis-diazoline, mixturesof about 75% [60]-bis-diazoline and about 25% [70]-bis-diazoline,mixtures of about 65% [60]-bis-diazoline and about 35%[70]-bis-diazoline, mixtures of about 55% [60]-bis-diazoline and about45% [70]-bis-diazoline, mixtures of about 45% [60]-bis-diazoline andabout 55% [70]-bis-diazoline, mixtures of about 35% [60]-bis-diazolineand about 65% [70]-bis-diazoline, mixtures of about 25%[60]-bis-diazoline and about 75% [70]-bis-diazoline, mixtures of about15% [60]-bis-diazoline and about 85% [70]-bis-diazoline, and mixtures ofabout 5% [60]-bis-diazoline and about 95% [70]-bis-diazoline.

The compositions described herein may comprise mixtures of C₆₀ and C₇₀fullerenes each derivatized with azafulleroid, including: mixtures ofabout 95% [60]-bis-azafulleroid and about 5% [70]-bis-azafulleroid,mixtures of about 85% [60]-bis-azafulleroid and about 15%[70]-bis-azafulleroid, mixtures of about 75% [60]-bis-azafulleroid andabout 25% [70]-bis-azafulleroid, mixtures of about 65%[60]-bis-azafulleroid and about 35% [70]-bis-azafulleroid, mixtures ofabout 55% [60]-bis-azafulleroid and about 45% [70]-bis-azafulleroid,mixtures of about 45% [60]-bis-azafulleroid and about 55%[70]-bis-azafulleroid, mixtures of about 35% [60]-bis-azafulleroid andabout 65% [70]-bis-azafulleroid, mixtures of about 25%[60]-bis-azafulleroid and about 75% [70]-bis-azafulleroid, mixtures ofabout 15% [60]-bis-azafulleroid and about 85% [70]-bis-azafulleroid, andmixtures of about 5% [60]-bis-azafulleroid and about 95%[70]-bis-azafulleroid.

The compositions described herein may comprise mixtures of C₆₀ and C₇₀fullerenes each derivatized with ketolactam, including: mixtures ofabout 95% [60]-bis-ketolactam and about 5% [70]-bis-ketolactam, mixturesof about 85% [60]-bis-ketolactam and about 15% [70]-bis-ketolactam,mixtures of about 75% [60]-bis-ketolactam and about 25%[70]-bis-ketolactam, mixtures of about 65% [60]-bis-ketolactam and about35% [70]-bis-ketolactam, mixtures of about 55% [60]-bis-ketolactam andabout 45% [70]-bis-ketolactam, mixtures of about 45% [60]-bis-ketolactamand about 55% [70]-bis-ketolactam, mixtures of about 35%[60]-bis-ketolactam and about 65% [70]-bis-ketolactam, mixtures of about25% [60]-bis-ketolactam and about 75% [70]-bis-ketolactam, mixtures ofabout 15% [60]-bis-ketolactam and about 85% [70]-bis-ketolactam, andmixtures of about 5% [60]-bis-ketolactam and about 95%[70]-bis-ketolactam.

The compositions described herein may comprise mixtures of C₆₀ and C₇₀fullerenes each derivatized with Diels Alder, including: mixtures ofabout 95% [60]-bis-Diels Alder and about 5% [70]-bis-Diels Alder,mixtures of about 85% [60]-bis-Diels Alder and about 15% [70]-bis-DielsAlder, mixtures of about 75% [60]-bis-Diels Alder and about 25%[70]-bis-Diels Alder, mixtures of about 65% [60]-bis-Diels Alder andabout 35% [70]-bis-Diels Alder, mixtures of about 55% [60]-bis-DielsAlder and about 45% [70]-bis-Diels Alder, mixtures of about 45%[60]-bis-Diels Alder and about 55% [70]-bis-Diels Alder, mixtures ofabout 35% [60]-bis-Diels Alder and about 65% [70]-bis-Diels Alder,mixtures of about 25% [60]-bis-Diels Alder and about 75% [70]-bis-DielsAlder, mixtures of about 15% [60]-bis-Diels Alder and about 85%[70]-bis-Diels Alder, and mixtures of about 5% [60]-bis-Diels Alder andabout 95% [70]-bis-Diels Alder.

Mixtures of C₆₀ and C₇₀ Fullerene Bis-Derivatives, Derivatized withDifferent Entities

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with PCBM and C₇₀ fullerenes derivatized withThCBM, including: mixtures of about 95% [60]-bis-PCBM and about 5%[70]-bis-ThCBM, mixtures of about 85% [60]-bis-PCBM and about 15%[70]-bis-ThCBM, mixtures of about 75% [60]-bis-PCBM and about 25%[70]-bis-ThCBM, mixtures of about 65% [60]-bis-PCBM and about 35%[70]-bis-ThCBM, mixtures of about 55% [60]-bis-PCBM and about 45%[70]-bis-ThCBM, mixtures of about 45% [60]-bis-PCBM and about 55%[70]-bis-ThCBM, mixtures of about 35% [60]-bis-PCBM and about 65%[70]-bis-ThCBM, mixtures of about 25% [60]-bis-PCBM and about 75%[70]-bis-ThCBM, mixtures of about 15% [60]-bis-PCBM and about 85%[70]-bis-ThCBM, and mixtures of about 5% [60]-bis-PCBM and about 95%[70]-bis-ThCBM.

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with PCBM and C₇₀ fullerenes derivatized withPrato adducts, including: mixtures of about 95% [60]-bis-PCBM and about5% [70]-bis-Prato, mixtures of about 85% [60]-bis-PCBM and about 15%[70]-bis-Prato, mixtures of about 75% [60]-bis-PCBM and about 25%[70]-bis-Prato, mixtures of about 65% [60]-bis-PCBM and about 35%[70]-bis-Prato, mixtures of about 55% [60]-bis-PCBM and about 45%[70]-bis-Prato, mixtures of about 45% [60]-bis-PCBM and about 55%[70]-bis-Prato, mixtures of about 35% [60]-bis-PCBM and about 65%[70]-bis-Prato, mixtures of about 25% [60]-bis-PCBM and about 75%[70]-bis-Prato, mixtures of about 15% [60]-bis-PCBM and about 85%[70]-bis-Prato, and mixtures of about 5% [60]-bis-PCBM and about 95%[70]-bis-Prato.

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with ThCBM and C₇₀ fullerenes derivatized withPCBM, including: mixtures of about 95% [60]-bis-ThCBM and about 5%[70]-bis-PCBM, mixtures of about 85% [60]-bis-ThCBM and about 15%[70]-bis-PCBM, mixtures of about 75% [60]-bis-ThCBM and about 25%[70]-bis-PCBM, mixtures of about 65% [60]-bis-ThCBM and about 35%[70]-bis-PCBM, mixtures of about 55% [60]-bis-ThCBM and about 45%[70]-bis-PCBM, mixtures of about 45% [60]-bis-ThCBM and about 55%[70]-bis-PCBM, mixtures of about 35% [60]-bis-ThCBM and about 65%[70]-bis-PCBM, mixtures of about 25% [60]-bis-ThCBM and about 75%[70]-bis-PCBM, mixtures of about 15% [60]-bis-ThCBM and about 85%[70]-bis-PCBM, and mixtures of about 5% [60]-bis-ThCBM and about 95%[70]-bis-PCBM.

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with ThCBM and C₇₀ fullerenes derivatized withPrato adducts, including: mixtures of about 95% [60]-bis-ThCBM and about5% [70]-bis-Prato, mixtures of about 85% [60]-bis-ThCBM and about 15%[70]-bis-Prato, mixtures of about 75% [60]-bis-ThCBM and about 25%[70]-bis-Prato, mixtures of about 65% [60]-bis-ThCBM and about 35%[70]-bis-Prato, mixtures of about 55% [60]-bis-ThCBM and about 45%[70]-bis-Prato, mixtures of about 45% [60]-bis-ThCBM and about 55%[70]-bis-Prato, mixtures of about 35% [60]-bis-ThCBM and about 65%[70]-bis-Prato, mixtures of about 25% [60]-bis-ThCBM and about 75%[70]-bis-Prato, mixtures of about 15% [60]-bis-ThCBM and about 85%[70]-bis-Prato, and mixtures of about 5% [60]-bis-ThCBM and about 95%[70]-bis-Prato.

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with Prato adducts and C₇₀ fullerenes derivatizedwith PCBM, including: mixtures of about 95% [60]-bis-Prato and about 5%[70]-bis-PCBM, mixtures of about 85% [60]-bis-Prato and about 15%[70]-bis-PCBM, mixtures of about 75% [60]-bis-Prato and about 25%[70]-bis-PCBM, mixtures of about 65% [60]-bis-Prato and about 35%[70]-bis-PCBM, mixtures of about 55% [60]-bis-Prato and about 45%[70]-bis-PCBM, mixtures of about 45% [60]-bis-Prato and about 55%[70]-bis-PCBM, mixtures of about 35% [60]-bis-Prato and about 65%[70]-bis-PCBM, mixtures of about 25% [60]-bis-Prato and about 75%[70]-bis-PCBM, mixtures of about 15% [60]-bis-Prato and about 85%[70]-bis-PCBM, and mixtures of about 5% [60]-bis-Prato and about 95%[70]-bis-PCBM.

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with Prato adducts and C₇₀ fullerenes derivatizedwith ThCBM, including: mixtures of about 95% [60]-bis-Prato and about 5%[70]-bis-ThCBM, mixtures of about 85% [60]-bis-Prato and about 15%[70]-bis-ThCBM, mixtures of about 75% [60]-bis-Prato and about 25%[70]-bis-ThCBM, mixtures of about 65% [60]-bis-Prato and about 35%[70]-bis-ThCBM, mixtures of about 55% [60]-bis-Prato and about 45%[70]-bis-ThCBM, mixtures of about 45% [60]-bis-Prato and about 55%[70]-bis-ThCBM, mixtures of about 35% [60]-bis-Prato and about 65%[70]-bis-ThCBM, mixtures of about 25% [60]-bis-Prato and about 75%[70]-bis-ThCBM, mixtures of about 15% [60]-bis-Prato and about 85%[70]-bis-ThCBM, and mixtures of about 5% [60]-bis-Prato and about 95%[70]-bis-ThCBM.

Mixtures of Bis-Derivatized and Unreacted C60 Fullerenes

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with PCBM and unreacted C₆₀ fullerenes,including: mixtures of about 97% [60]-bis-PCBM and about 3% [60], about87% [60]-bis-PCBM and about 13% [60], about 77% [60]-bis-PCBM and about23% [60], about 67% [60]-bis-PCBM and about 33% [60], about 57%[60]-bis-PCBM and about 43% [60], about 47% [60]-bis-PCBM and about 53%[60], about 37% [60]-bis-PCBM and about 63% [60], about 27%[60]-bis-PCBM and about 73% [60], about 17% [60]-bis-PCBM and about 83%[60], and about 7% [60]-bis-PCBM and about 93% [60].

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with ThCBM and unreacted C₆₀ fullerenes,including: mixtures of about 97% [60]-bis-ThCBM and about 3% [60], about87% [60]-bis-ThCBM and about 13% [60], about 77% [60]-bis-ThCBM andabout 23% [60], about 67% [60]-bis-ThCBM and about 33% [60], about 57%[60]-bis-ThCBM and about 43% [60], about 47% [60]-bis-ThCBM and about53% [60], about 37% [60]-bis-ThCBM and about 63% [60], about 27%[60]-bis-ThCBM and about 73% [60], about 17% [60]-bis-ThCBM and about83% [60], and about 7% [60]-bis-ThCBM and about 93% [60].

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with Prato adducts and unreacted C₆₀ fullerenes,including: mixtures of about 97% [60]-bis-Prato and about 3% [60], about87% [60]-bis-Prato and about 13% [60], about 77% [60]-bis-Prato andabout 23% [60], about 67% [60]-bis-Prato and about 33% [60], about 57%[60]-bis-Prato and about 43% [60], about 47% [60]-bis-Prato and about53% [60], about 37% [60]-bis-Prato and about 63% [60], about 27%[60]-bis-Prato and about 73% [60], about 17% [60]-bis-Prato and about83% [60], and about 7% [60]-bis-Prato and about 93% [60].

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with Bingel adducts and unreacted C₆₀ fullerenes,including: mixtures of about 97% [60]-bis-Bingel and about 3% [60],about 87% [60]-bis-Bingel and about 13% [60], about 77% [60]-bis-Bingeland about 23% [60], about 67% [60]-bis-Bingel and about 33% [60], about57% [60]-bis-Bingel and about 43% [60], about 47% [60]-bis-Bingel andabout 53% [60], about 37% [60]-bis-Bingel and about 63% [60], about 27%[60]-bis-Bingel and about 73% [60], about 17% [60]-bis-Bingel and about83% [60], and about 7% [60]-bis-Bingel and about 93% [60].

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with diazoline adducts and unreacted C₆₀fullerenes, including: mixtures of about 97% [60]-bis-diazoline andabout 3% [60], about 87% [60]-bis-diazoline and about 13% [60], about77% [60]-bis-diazoline and about 23% [60], about 67% [60]-bis-diazolineand about 33% [60], about 57% [60]-bis-diazoline and about 43% [60],about 47% [60]-bis-diazoline and about 53% [60], about 37%[60]-bis-diazoline and about 63% [60], about 27% [60]-bis-diazoline andabout 73% [60], about 17% [60]-bis-diazoline and about 83% [60], andabout 7% [60]-bis-diazoline and about 93% [60].

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with azafulleroid adducts and unreacted C₆₀fullerenes, including: mixtures of about 97% [60]-bis-azafulleroid andabout 3% [60], about 87% [60]-bis-azafulleroid and about 13% [60], about77% [60]-bis-azafulleroid and about 23% [60], about 67%[60]-bis-azafulleroid and about 33% [60], about 57%[60]-bis-azafulleroid and about 43% [60], about 47%[60]-bis-azafulleroid and about 53% [60], about 37%[60]-bis-azafulleroid and about 63% [60], about 27%[60]-bis-azafulleroid and about 73% [60], about 17%[60]-bis-azafulleroid and about 83% [60], and about 7%[60]-bis-azafulleroid and about 93% [60].

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with ketolactam adducts and unreacted C₆₀fullerenes, including: mixtures of about 97% [60]-bis-ketolactam andabout 3% [60], about 87% [60]-bis-ketolactam and about 13% [60], about77% [60]-bis-ketolactam and about 23% [60], about 67%[60]-bis-ketolactam and about 33% [60], about 57% [60]-bis-ketolactamand about 43% [60], about 47% [60]-bis-ketolactam and about 53% [60],about 37% [60]-bis-ketolactam and about 63% [60], about 27%[60]-bis-ketolactam and about 73% [60], about 17% [60]-bis-ketolactamand about 83% [60], and about 7% [60]-bis-ketolactam and about 93% [60].

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with Diels Alder adducts and unreacted C₆₀fullerenes, including: mixtures of about 97% [60]-bis-Diels Alder andabout 3% [60], about 87% [60]-bis-Diels Alder and about 13% [60], about77% [60]-bis-Diels Alder and about 23% [60], about 67% [60]-bis-DielsAlder and about 33% [60], about 57% [60]-bis-Diels Alder and about 43%[60], about 47% [60]-bis-Diels Alder and about 53% [60], about 37%[60]-bis-Diels Alder and about 63% [60], about 27% [60]-bis-Diels Alderand about 73% [60], about 17% [60]-bis-Diels Alder and about 83% [60],and about 7% [60]-bis-Diels Alder and about 93% [60].

Mixtures of Bis-Derivatized and Unreacted C70 Fullerenes

The compositions described herein may comprise mixtures of C₇₀fullerenes derivatized with PCBM and unreacted C₆₀ fullerenes,including: mixtures of about 97% [70]-bis-PCBM and about 3% [70], about87% [70]-bis-PCBM and about 13% [70], about 77% [70]-bis-PCBM and about23% [70], about 67% [70]-bis-PCBM and about 33% [70], about 57%[70]-bis-PCBM and about 43% [70], about 47% [70]-bis-PCBM and about 53%[70], about 37% [70]-bis-PCBM and about 63% [70], about 27%[70]-bis-PCBM and about 73% [70], about 17% [70]-bis-PCBM and about 83%[70], and about 7% [70]-bis-PCBM and about 93% [70].

The compositions described herein may comprise mixtures of C₇₀fullerenes derivatized with ThCBM and unreacted C₆₀ fullerenes,including: mixtures of about 97% [70]-bis-ThCBM and about 3% [70], about87% [70]-bis-ThCBM and about 13% [70], about 77% [70]-bis-ThCBM andabout 23% [70], about 67% [70]-bis-ThCBM and about 33% [70], about 57%[70]-bis-ThCBM and about 43% [70], about 47% [70]-bis-ThCBM and about53% [70], about 37% [70]-bis-ThCBM and about 63% [70], about 27%[70]-bis-ThCBM and about 73% [70], about 17% [70]-bis-ThCBM and about83% [70], and about 7% [70]-bis-ThCBM and about 93% [70].

The compositions described herein may comprise mixtures of C70fullerenes derivatized with Prato adducts and unreacted C₆₀ fullerenes,including: mixtures of about 97% [70]-bis-Prato and about 3% [70], about87% [70]-bis-Prato and about 13% [70], about 77% [70]-bis-Prato andabout 23% [70], about 67% [70]-bis-Prato and about 33% [70], about 57%[70]-bis-Prato and about 43% [70], about 47% [70]-bis-Prato and about53% [70], about 37% [70]-bis-Prato and about 63% [70], about 27%[70]-bis-Prato and about 73% [70], about 17% [70]-bis-Prato and about83% [70], and about 7% [70]-bis-Prato and about 93% [70].

The compositions described herein may comprise mixtures of C₇₀fullerenes derivatized with Bingel adducts and unreacted C₇₀ fullerenes,including: mixtures of about 97% [70]-bis-Bingel and about 3% [70],about 87% [70]-bis-Bingel and about 13% [70], about 77% [70]-bis-Bingeland about 23% [70], about 67% [70]-bis-Bingel and about 33% [70], about57% [70]-bis-Bingel and about 43% [70], about 47% [70]-bis-Bingel andabout 53% [70], about 37% [70]-bis-Bingel and about 63% [70], about 27%[70]-bis-Bingel and about 73% [70], about 17% [70]-bis-Bingel and about83% [70], and about 7% [70]-bis-Bingel and about 93% [70].

The compositions described herein may comprise mixtures of C₇₀fullerenes derivatized with diazoline adducts and unreacted C₇₀fullerenes, including: mixtures of about 97% [70]-bis-diazoline andabout 3% [70], about 87% [70]-bis-diazoline and about 13% [70], about77% [70]-bis-diazoline and about 23% [70], about 67% [70]-bis-diazolineand about 33% [70], about 57% [70]-bis-diazoline and about 43% [70],about 47% [70]-bis-diazoline and about 53% [70], about 37%[70]-bis-diazoline and about 63% [70], about 27% [70]-bis-diazoline andabout 73% [70], about 17% [70]-bis-diazoline and about 83% [70], andabout 7% [70]-bis-diazoline and about 93% [70].

The compositions described herein may comprise mixtures of C₇₀fullerenes derivatized with azafulleroid adducts and unreacted C₇₀fullerenes, including: mixtures of about 97% [70]-bis-azafulleroid andabout 3% [70], about 87% [70]-bis-azafulleroid and about 13% [70], about77% [70]-bis-azafulleroid and about 23% [70], about 67%[70]-bis-azafulleroid and about 33% [70], about 57%[70]-bis-azafulleroid and about 43% [70], about 47%[70]-bis-azafulleroid and about 53% [70], about 37%[70]-bis-azafulleroid and about 63% [70], about 27%[70]-bis-azafulleroid and about 73% [70], about 17%[70]-bis-azafulleroid and about 83% [70], and about 7%[70]-bis-azafulleroid and about 93% [70].

The compositions described herein may comprise mixtures of C₇₀fullerenes derivatized with ketolactam adducts and unreacted C₇₀fullerenes, including: mixtures of about 97% [70]-bis-ketolactam andabout 3% [70], about 87% [70]-bis-ketolactam and about 13% [70], about77% [70]-bis-ketolactam and about 23% [70], about 67%[70]-bis-ketolactam and about 33% [70], about 57% [70]-bis-ketolactamand about 43% [70], about 47% [70]-bis-ketolactam and about 53% [70],about 37% [70]-bis-ketolactam and about 63% [70], about 27%[70]-bis-ketolactam and about 73% [70], about 17% [70]-bis-ketolactamand about 83% [70], and about 7% [70]-bis-ketolactam and about 93% [70].

The compositions described herein may comprise mixtures of C₇₀fullerenes derivatized with Diels Alder adducts and unreacted C₇₀fullerenes, including: mixtures of about 97% [70]-bis-Diels Alder andabout 3% [70], about 87% [70]-bis-Diels Alder and about 13% [70], about77% [70]-bis-Diels Alder and about 23% [70], about 67% [70]-bis-DielsAlder and about 33% [70], about 57% [70]-bis-Diels Alder and about 43%[70], about 47% [70]-bis-Diels Alder and about 53% [70], about 37%[70]-bis-Diels Alder and about 63% [70], about 27% [70]-bis-Diels Alderand about 73% [70], about 17% [70]-bis-Diels Alder and about 83% [70],and about 7% [70]-bis-Diels Alder and about 93% [70].

Mixtures of C₆₀ Derivatized with Different Entities

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with PCBM and C₆₀ fullerenes derivatized withThCBM, including: mixtures of about 95% [60]PCBM and about 5% [60]ThCBM,mixtures of about 85% [60]PCBM and about 15% [60]ThCBM, mixtures ofabout 75% [60]PCBM and about 25% [60]ThCBM, mixtures of about 65%[60]PCBM and about 35% [60]ThCBM, mixtures of about 55% [60]PCBM andabout 45% [60]ThCBM, mixtures of about 45% [60]PCBM and about 55%[60]ThCBM, mixtures of about 35% [60]PCBM and about 65% [60]ThCBM,mixtures of about 25% [60]PCBM and about 75% [60]ThCBM, mixtures ofabout 15% [60]PCBM and about 85% [60]ThCBM, and mixtures of about 5%[60]PCBM and about 95% [60]ThCBM.

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with PCBM and C₆₀ fullerenes derivatized withPrato adducts, including: mixtures of about 95% [60]PCBM and about 5%[60]Prato, mixtures of about 85% [60]PCBM and about 15% [60]Prato,mixtures of about 75% [60]PCBM and about 25% [60]Prato, mixtures ofabout 65% [60]PCBM and about 35% [60]Prato, mixtures of about 55%[60]PCBM and about 45% [60]Prato, mixtures of about 45% [60]PCBM andabout 55% [60]Prato, mixtures of about 35% [60]PCBM and about 65%[60]Prato, mixtures of about 25% [60]PCBM and about 75% [60]Prato,mixtures of about 15% [60]PCBM and about 85% [60]Prato, and mixtures ofabout 5% [60]PCBM and about 95% [60]Prato.

The compositions described herein may comprise mixtures of C₆₀fullerenes derivatized with ThCBM and C₆₀ fullerenes derivatized withPrato adducts, including: mixtures of about 95% [60]ThCBM and about 5%[60]Prato, mixtures of about 85% [60]ThCBM and about 15% [60]Prato,mixtures of about 75% [60]ThCBM and about 25% [60]Prato, mixtures ofabout 65% [60]ThCBM and about 35% [60]Prato, mixtures of about 55%[60]ThCBM and about 45% [60]Prato, mixtures of about 45% [60]ThCBM andabout 55% [60]Prato, mixtures of about 35% [60]ThCBM and about 65%[60]Prato, mixtures of about 25% [60]ThCBM and about 75% [60]Prato,mixtures of about 15% [60]ThCBM and about 85% [60]Prato, and mixtures ofabout 5% [60]ThCBM and about 95% [60]Prato.

Mixtures of C₇₀ Derivatized with Different Entities

The compositions described herein may comprise mixtures of C₇₀fullerenes derivatized with PCBM and C₇₀ fullerenes derivatized withThCBM, including: mixtures of about 95% [70]PCBM and about 5% [70]ThCBM,mixtures of about 85% [70]PCBM and about 15% [70]ThCBM, mixtures ofabout 75% [70]PCBM and about 25% [70]ThCBM, mixtures of about 65%[70]PCBM and about 35% [70]ThCBM, mixtures of about 55% [70]PCBM andabout 45% [70]ThCBM, mixtures of about 45% [70]PCBM and about 55%[70]ThCBM, mixtures of about 35% [70]PCBM and about 65% [70]ThCBM,mixtures of about 25% [70]PCBM and about 75% [70]ThCBM, mixtures ofabout 15% [70]PCBM and about 85% [70]ThCBM, and mixtures of about 5%[70]PCBM and about 95% [70]ThCBM.

The compositions described herein may comprise mixtures of C₇₀fullerenes derivatized with PCBM and C₇₀ fullerenes derivatized withPrato adducts, including: mixtures of about 95% [70]PCBM and about 5%[70]Prato, mixtures of about 85% [70]PCBM and about 15% [70]Prato,mixtures of about 75% [70]PCBM and about 25% [70]Prato, mixtures ofabout 65% [70]PCBM and about 35% [70]Prato, mixtures of about 55%[70]PCBM and about 45% [70]Prato, mixtures of about 45% [70]PCBM andabout 55% [70]Prato, mixtures of about 35% [70]PCBM and about 65%[70]Prato, mixtures of about 25% [70]PCBM and about 75% [70]Prato,mixtures of about 15% [70]PCBM and about 85% [70]Prato, and mixtures ofabout 5% [70]PCBM and about 95% [70]Prato.

The compositions described herein may comprise mixtures of C₇₀fullerenes derivatized with ThCBM and C₇₀ fullerenes derivatized withPrato adducts, including: mixtures of about 95% [70]ThCBM and about 5%[70]Prato, mixtures of about 85% [70]ThCBM and about 15% [70]Prato,mixtures of about 75% [70]ThCBM and about 25% [70]Prato, mixtures ofabout 65% [70]ThCBM and about 35% [70]Prato, mixtures of about 55%[70]ThCBM and about 45% [70]Prato, mixtures of about 45% [70]ThCBM andabout 55% [70]Prato, mixtures of about 35% [70]ThCBM and about 65%[70]Prato, mixtures of about 25% [70]ThCBM and about 75% [70]Prato,mixtures of about 15% [70]ThCBM and about 85% [70]Prato, and mixtures ofabout 5% [70]ThCBM and about 95% [70]Prato.

The compositions described herein may also comprise ternary, quaternary,and higher mixtures of unreacted C₆₀ and C₇₀, derivatized C₆₀ and C₇₀,and higher order adduct derivatives, comprising bis, tris, ter, andhigher. The ratios of adducts produced during synthesis can be modifiedby varying the amount of the BBMT precursor. Removal of multi-adductcompounds may be accomplished on a silica gel column.

Additional Embodiments

The present invention is described below by reference to certainembodiments. This description is not meant to limit the scope of theinvention, but to convey the essence of the invention. Additionalembodiments may be readily envisioned by one of ordinary skill in theart, and such embodiments fall within the scope of the invention.

One aspect of the invention relates to the use as a semiconductor afullerene derivative mixture which has a composition resulting from theuse of mixed fullerenes to perform the synthesis of the fullerenederivatives, wherein the mixed fullerenes composition is as producedfrom a fullerene synthesis process such as but not limited toarc-vaporization, laser ablation, or combustion synthesis.

In certain embodiments, the present invention relates to aforementionedinvention, wherein one or more fullerene species has been removed fromthe as-produced fullerene mixture described above.

In certain embodiments, the present invention relates to aforementionedinvention, wherein fullerenes higher in molecular weight than C₇₀ havebeen removed from the as-produced fullerene mixture.

In certain embodiments, the present invention relates to aforementionedinvention, wherein one or more fullerene derivatives is removed from theresulting fullerene derivative mixture made from the as-producedfullerene mixture.

In certain embodiments, the present invention relates to aforementionedinvention, wherein the fullerene derivatives of fullerenes higher inmolecular weight than C₇₀ have been removed.

Another aspect of the invention relates to the use as a semiconductorcompound of a mixture comprising C₆₀ methanofullerene derivatives andC₇₀ methanofullerene derivatives where the molar percentage of each isin the range of 1% to 99%.

In certain embodiments, the present invention relates to aforementionedinvention, wherein the fullerene derivatives arePhenyl-C₆₁-Butyric-Acid-Methyl-Ester orPhenyl-C₇₁-Butyric-Acid-Methyl-Ester Methanofullerenes,Thiophenyl-C₆₁-Butyric-Acid-Methyl-Ester orThiophenyl-C₇₁-Butyric-Acid-Methyl-Ester methanofullerenes, andPrato-C₆₁- or Prato-C₇₁-fullerenes.

Another aspect of the invention relates to a photodiode device whereinthe n-type semiconductor comprised is as described above.

Another aspect of the invention relates to a transistor device whereinthe n-type semiconductor comprised is as described above.

Another aspect of the invention relates to an ambipolar transistordevice wherein the ambipolar semiconductor comprised is as describedabove.

In certain embodiments, the present invention relates to aforementionedinvention, wherein the composition of the C₆₀ fullerene derivative is inthe range of 20% to 90% and the composition of the C₇₀ fullerenederivative is in the range of 9% to 79%.

In certain embodiments, the present invention relates to aforementionedinvention, wherein the molar percentage of the C₆₀ fullerene derivativeis in the range 40% to 80%, and the molar percentage of the C₇₀fullerene derivative is in the range of 19% to 59%.

In certain embodiments, the present invention relates to aforementionedinvention, wherein the molar percentage of underivatized C₆₀ is in therange of 1% to 49% and the combined molar percentage of C₆₀ and C₇₀derivatives is in the range of 50% to 98%.

In certain embodiments, the present invention relates to aforementionedinvention, wherein the derivatized C₆₀ and/or C₇₀ comprises mono-, bis-,and tris-adducts.

The use as a semiconductor compound of a mixture of C₈₄ fullerenederivatives in a blend with C₇₀, C₇₆, and C₇₈ derivatives either inconjunction or alone.

Another aspect of the invention relates to a transistor device whereinthe n-type semiconductor is as described above.

DEFINITIONS

For convenience, certain terms employed in the specification, examples,and appended claims are collected here.

The term “addend moieties” refers here to the chemical addend which isbonded to the fullerene core through the synthesis on a fullerenemixture. For example, the phenyl-butyric-acid-methyl-ester moiety ofPCBM is referred to here as an addend moiety.

The term “fullerene chemical derivatives,” e.g., C60 chemicalderivatives, C70 chemical derivatives, C84 chemical derivatives refer tothe addition of chemically bonded addends to the fullerene core, whichcan be accomplished by many chemical synthesis techniques, which arewell known in the art and termed “fullerene chemistry.” Common examplesare methanofullerene chemical derivatives (e.g., PCBM), Prato chemicalderivatives, Bingel chemical derivatives, diazoline chemicalderivatives, azafulleroid chemical derivatives, ketolactam chemicalderivatives, and Diels Alder chemical derivatives. In the case offullerenes C70 and higher in molecular weight, the fullerene chemicalderivative may be present in one or more isomeric forms, such as isknown in the art for [70]PCBM and [84]PCBM. In the case of bis andhigher adducts, even more isomeric forms may be present.

The term “class,” e.g., “ . . . same class of derivatives . . . ” refersto a set or group of chemical derivatives that share a common addendmoiety. Common examples are the PCBM class of chemical derivatives, theThCBM class of chemical derivatives, and the Prato class of chemicalderivatives.

The term “fullerene mixture” refers to a mixture of fullerenes, e.g.,C60, C70, C76, C78, C84, and traces of other fullerenes, such as formedby fullerene production processes known in the art. Common fullereneproduction processes are arc-synthesis, combustion, laser ablation,among others. All fullerene processes produce a distribution offullerenes of various molecular weight. For example, arc-synthesistypically produces ca. 60%-90% C60, 10%-30% C70, and 1%-10% fullereneshigher in molecular weight than C70. Combustion processes producesomewhat higher proportions of fullerenes C70 and higher, and can evenproduce more C70 than C60 proportionately. In this context, variousother impurities may be present in the fullerene mixture used in thesynthesis described herein, such as oxides and dimers of fullerenes, andamorphous carbon, in various amounts.

The term “synthesis of a fullerene mixture” refers to carrying out atypical fullerene chemical synthesis as is well known in the art, suchas diazoalkane addition, Prato reaction, Bingel, etc. such as commonlycarried out on pure grades of e.g., C60, C70, C84, etc., using afullerene mixture as a reactant in place of the pure grade of fullerene.

The term “multi-adduct” chemical derivatives refer to bis, tris, ter-,etc. adducts, where more than one chemical addend of the same type isbonded to the fullerene core. For example, as a by-product ofmethanofullerene synthesis using diazoalkane addition, such as thesynthesis of PCBM, roughly 10%-20% yield (based on fullerene reactant)of bis-adduct will be formed, and 1-2% yield of tris-adduct, and tracesof tris and higher adducts, due to the multitude and symmetry ofreactive sites on the fullerene (C60 and C70) core. One can alsoincrease or decrease the yield of multi-adducts by varying equivalentsof reactant, for example increasing the concentration of reactant beingadded to the fullerene core.

The term “fullerenes higher in molecular weight than C70” refers tofullerenes with a greater number of carbons than 70, such as C76, C78,and C84, but. “Chemical Derivatives” of these are for example in thecase of PCBM synthesis, [76]PCBM, [78]PCBM, and [84]PCBM, which areformed as a by-product of reaction if C76, C78, and C84 are present inthe reactant fullerene mixture, which they typically are. The fullereneshigher than C70 will react during the addend formation and remainpresent to some degree in the initial reaction product. Forarc-synthesized fullerenes, the percentage of fullerenes higher inmolecular weight than C70 are typically 3-6% of total fullerene content,and are primarily C76, C78, and C84. Combustion produced fullerenestypically have higher percentages of these fullerenes, and can be15%-20% or higher of total fullerene content, and include otherfullerenes higher in molecular weight than C70, such as C82, C90, etc.

The term “oxides” of fullerenes and fullerene derivatives refers to theepoxides and other products, which can be single or multi-addendproducts, of photochemical degradation of fullerenes and fullerenederivatives which are well known in the art to form when fullerenes areexposed to air and light. Minimization of the formation of thesecompounds is accomplished typically by reaction under inert atmosphere(e.g., N2), though typically some amount are present in any fullerenesynthesis product. “Fullerene derivative oxides” refer to for examplePCBM reacting with light and air to form a product consisting of one ormore epoxides bonded to the fullerene core in addition to thephenyl-butyric-acid-methyl ester addend, or to the addition of thephenyl-butyric-acid-methyl ester addend to a fullerene alreadycontaining an epoxide addend. The fullerene oxides may be present in thefullerene reactant, and thus lead to derivative oxides, or the oxidesmay form as a result of the fullerene synthesis.

The term “dimer” refer to the formation of fullerene-fullerene bondsleading to, in the case of fullerenes, C60-C60, C70-70, and the like,which are spontaneously formed during the fullerene production processor later. These compounds are typically seen in some amount in fullerenesources. Dimers of fullerene derivatives can also form by addition ofthe addend to a dimer of the fullerene reactant, or spontaneously as aby-product of the fullerene chemical derivative synthesis. Dimers canalso be oxidized.

The term “solution processing” refers to the technique well known in theart of dissolving or suspending an n-type or p-type semiconductor orcombination of these and applying this solution to a surface, where thedeposited solution is then allowed to dry. Techniques commonly used forthis are spin-coating, doctor-blading, printing techniques (such as inkjet printing, roll-to-roll printing, silkscreening) or the like.

The term “heteroatom” is art-recognized and refers to an atom of anyelement other than carbon or hydrogen. Illustrative heteroatoms includeboron, nitrogen, oxygen, phosphorus, sulfur and selenium.

The term “alkyl” is art-recognized, and includes saturated aliphaticgroups, including straight-chain alkyl groups, branched-chain alkylgroups, cycloalkyl (alicyclic) groups, alkyl substituted cycloalkylgroups, and cycloalkyl substituted alkyl groups. In certain embodiments,a straight chain or branched chain alkyl has about 30 or fewer carbonatoms in its backbone (e.g., C₁-C₃₀ for straight chain, C₃-C₃₀ forbranched chain), and alternatively, about 20 or fewer. Likewise,cycloalkyls have from about 3 to about 10 carbon atoms in their ringstructure, and alternatively about 5, 6 or 7 carbons in the ringstructure.

Unless the number of carbons is otherwise specified, “lower alkyl”refers to an alkyl group, as defined above, but having from one to aboutten carbons, alternatively from one to about six carbon atoms in itsbackbone structure. Likewise, “lower alkenyl” and “lower alkynyl” havesimilar chain lengths.

The term “aralkyl” is art-recognized and refers to an alkyl groupsubstituted with an aryl group (e.g., an aromatic or heteroaromaticgroup).

The terms “alkenyl” and “alkynyl” are art-recognized and refer tounsaturated aliphatic groups analogous in length and possiblesubstitution to the alkyls described above, but that contain at leastone double or triple bond respectively.

The term “aryl” is art-recognized and refers to 5-, 6- and 7-memberedsingle-ring aromatic groups that may include from zero to fourheteroatoms, for example, benzene, naphthalene, anthracene, pyrene,pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole,pyrazole, pyridine, pyrazine, pyridazine and pyrimidine, and the like.Those aryl groups having heteroatoms in the ring structure may also bereferred to as “aryl heterocycles” or “heteroaromatics.” The aromaticring may be substituted at one or more ring positions with suchsubstituents as described above, for example, halogen, azide, alkyl,aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino, nitro,sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl,silyl, ether, alkylthio, sulfonyl, sulfonamido, ketone, aldehyde, ester,heterocyclyl, aromatic or heteroaromatic moieties, —CF₃, —CN, or thelike. The term “aryl” also includes polycyclic ring systems having twoor more cyclic rings in which two or more carbons are common to twoadjoining rings (the rings are “fused rings”) wherein at least one ofthe rings is aromatic, e.g., the other cyclic rings may be cycloalkyls,cycloalkenyls, cycloalkynyls, aryls and/or heterocyclyls.

The term “adduct” is art-recognized and refers to a new molecularspecies (AB) formed by direct combination of two separate molecularentities (A+B). The term “bis-adduct” refers to molecular species AB₂.The term “tris-adduct” refers to molecular species AB₃. The terms“adduct” and “derivative” are used interchangeably herein.

The terms ortho, meta and para are art-recognized and refer to 1,2-,1,3- and 1,4-disubstituted benzenes, respectively. For example, thenames 1,2-dimethylbenzene and ortho-dimethylbenzene are synonymous.

The terms “heterocyclyl”, “heteroaryl”, or “heterocyclic group” areart-recognized and refer to 3- to about 10-membered ring structures,alternatively 3- to about 7-membered rings, whose ring structuresinclude one to four heteroatoms. Heterocycles may also be polycycles.Heterocyclyl groups include, for example, thiophene, thianthrene, furan,pyran, isobenzofuran, chromene, xanthene, phenoxanthene, pyrrole,imidazole, pyrazole, isothiazole, isoxazole, pyridine, pyrazine,pyrimidine, pyridazine, indolizine, isoindole, indole, indazole, purine,quinolizine, isoquinoline, quinoline, phthalazine, naphthyridine,quinoxaline, quinazoline, cinnoline, pteridine, carbazole, carboline,phenanthridine, acridine, pyrimidine, phenanthroline, phenazine,phenarsazine, phenothiazine, furazan, phenoxazine, pyrrolidine, oxolane,thiolane, oxazole, piperidine, piperazine, morpholine, lactones, lactamssuch as azetidinones and pyrrolidinones, sultams, sultones, and thelike. The heterocyclic ring may be substituted at one or more positionswith such substituents as described above, as for example, halogen,alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, amino, nitro,sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl,silyl, ether, alkylthio, sulfonyl, ketone, aldehyde, ester, aheterocyclyl, an aromatic or heteroaromatic moiety, —CF₃, —CN, or thelike.

The terms “polycyclyl” or “polycyclic group” are art-recognized andrefer to two or more rings (e.g., cycloalkyls, cycloalkenyls,cycloalkynyls, aryls and/or heterocyclyls) in which two or more carbonsare common to two adjoining rings, e.g., the rings are “fused rings”.Rings that are joined through non-adjacent atoms are termed “bridged”rings. Each of the rings of the polycycle may be substituted with suchsubstituents as described above, as for example, halogen, alkyl,aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, amino, nitro,sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl,silyl, ether, alkylthio, sulfonyl, ketone, aldehyde, ester, aheterocyclyl, an aromatic or heteroaromatic moiety, —CF₃, —CN, or thelike.

The term “carbocycle” is art-recognized and refers to an aromatic ornon-aromatic ring in which each atom of the ring is carbon.

The term “nitro” is art-recognized and refers to —NO₂; the term“halogen” is art-recognized and refers to —F, —Cl, —Br or —I; the term“sulfhydryl” is art-recognized and refers to —SH; the term “hydroxyl”means —OH; and the term “sulfonyl” is art-recognized and refers to —SO₂⁻. “Halide” designates the corresponding anion of the halogens, and“pseudohalide” has the definition set forth on 560 of “AdvancedInorganic Chemistry” by Cotton and Wilkinson.

The terms “amine” and “amino” are art-recognized and refer to bothunsubstituted and substituted amines, e.g., a moiety that may berepresented by the general formulas:

wherein R50, R51 and R52 each independently represent a hydrogen, analkyl, an alkenyl, —(CH₂)_(m)—R61, or R50 and R51, taken together withthe N atom to which they are attached complete a heterocycle having from4 to 8 atoms in the ring structure; R61 represents an aryl, acycloalkyl, a cycloalkenyl, a heterocycle or a polycycle; and m is zeroor an integer in the range of 1 to 8. In certain embodiments, only oneof R50 or R51 may be a carbonyl, e.g., R50, R51 and the nitrogentogether do not form an imide. In other embodiments, R50 and R51 (andoptionally R52) each independently represent a hydrogen, an alkyl, analkenyl, or —(CH₂)_(m)—R61. Thus, the term “alkylamine” includes anamine group, as defined above, having a substituted or unsubstitutedalkyl attached thereto, i.e., at least one of R50 and R51 is an alkylgroup.

The term “acylamino” is art-recognized and refers to a moiety that maybe represented by the general formula:

wherein R50 is as defined above, and R54 represents a hydrogen, analkyl, an alkenyl or —(CH₂)_(m)—R61, where m and R61 are as definedabove.

The term “amido” is art recognized as an amino-substituted carbonyl andincludes a moiety that may be represented by the general formula:

wherein R50 and R51 are as defined above. Certain embodiments of theamide in the present invention will not include imides which may beunstable.

The term “alkylthio” refers to an alkyl group, as defined above, havinga sulfur radical attached thereto. In certain embodiments, the“alkylthio” moiety is represented by one of —S-alkyl, —S-alkenyl,—S-alkynyl, and —S—(CH₂)_(m)—R61, wherein m and R61 are defined above.Representative alkylthio groups include methylthio, ethyl thio, and thelike.

The term “carboxyl” is art recognized and includes such moieties as maybe represented by the general formulas:

wherein X50 is a bond or represents an oxygen or a sulfur, and R55 andR56 represents a hydrogen, an alkyl, an alkenyl, —(CH₂)_(m)—R61 or apharmaceutically acceptable salt, R56 represents a hydrogen, an alkyl,an alkenyl or —(CH₂)_(m)—R61, where m and R61 are defined above. WhereX50 is an oxygen and R55 or R56 is not hydrogen, the formula representsan “ester”. Where X50 is an oxygen, and R55 is as defined above, themoiety is referred to herein as a carboxyl group, and particularly whenR55 is a hydrogen, the formula represents a “carboxylic acid”. Where X50is an oxygen, and R56 is hydrogen, the formula represents a “formate”.In general, where the oxygen atom of the above formula is replaced bysulfur, the formula represents a “thiolcarbonyl” group. Where X50 is asulfur and R55 or R56 is not hydrogen, the formula represents a“thiolester.” Where X50 is a sulfur and R55 is hydrogen, the formularepresents a “thiolcarboxylic acid.” Where X50 is a sulfur and R56 ishydrogen, the formula represents a “thiolformate.” On the other hand,where X50 is a bond, and R55 is not hydrogen, the above formularepresents a “ketone” group. Where X50 is a bond, and R55 is hydrogen,the above formula represents an “aldehyde” group.

The terms “alkoxyl” or “alkoxy” are art-recognized and refer to an alkylgroup, as defined above, having an oxygen radical attached thereto.Representative alkoxyl groups include methoxy, ethoxy, propyloxy,tert-butoxy and the like. An “ether” is two hydrocarbons covalentlylinked by an oxygen. Accordingly, the substituent of an alkyl thatrenders that alkyl an ether is or resembles an alkoxyl, such as may berepresented by one of —O-alkyl, —O-alkenyl, —O-alkenyl,—O—(CH₂)_(m)—R61, where m and R61 are described above.

The term “sulfonate” is art recognized and refers to a moiety that maybe represented by the general formula:

in which R57 is an electron pair, hydrogen, alkyl, cycloalkyl, or aryl.

The term “sulfate” is art recognized and includes a moiety that may berepresented by the general formula:

in which R57 is as defined above.

The term “sulfonamido” is art recognized and includes a moiety that maybe represented by the general formula:

in which R50 and R56 are as defined above.

The term “sulfamoyl” is art-recognized and refers to a moiety that maybe represented by the general formula:

in which R50 and R51 are as defined above.

The term “sulfonyl” is art-recognized and refers to a moiety that may berepresented by the general formula:

in which R58 is one of the following: hydrogen, alkyl, alkenyl, alkynyl,cycloalkyl, heterocyclyl, aryl or heteroaryl.

The term “sulfoxido” is art-recognized and refers to a moiety that maybe represented by the general formula:

in which R58 is defined above.

The term “phosphoryl” is art-recognized and may in general berepresented by the formula:

wherein Q50 represents S or O, and R59 represents hydrogen, a loweralkyl or an aryl. When used to substitute, e.g., an alkyl, thephosphoryl group of the phosphorylalkyl may be represented by thegeneral formulas:

wherein Q50 and R59, each independently, are defined above, and Q51represents O, S or N. When Q50 is S, the phosphoryl moiety is a“phosphorothioate”.

The term “phosphoramidite” is art-recognized and may be represented inthe general formulas:

wherein Q51, R50, R51 and R59 are as defined above.

The term “phosphonamidite” is art-recognized and may be represented inthe general formulas:

wherein Q51, R50, R51 and R59 are as defined above, and R60 represents alower alkyl or an aryl.

Analogous substitutions may be made to alkenyl and alkynyl groups toproduce, for example, aminoalkenyls, aminoalkynyls, amidoalkenyls,amidoalkynyls, iminoalkenyls, iminoalkynyls, thioalkenyls, thioalkynyls,carbonyl-substituted alkenyls or alkynyls.

The definition of each expression, e.g. alkyl, m, n, and the like, whenit occurs more than once in any structure, is intended to be independentof its definition elsewhere in the same structure.

The term “selenoalkyl” is art-recognized and refers to an alkyl grouphaving a substituted seleno group attached thereto. Exemplary“selenoethers” which may be substituted on the alkyl are selected fromone of —Se-alkyl, —Se-alkenyl, —Se-alkynyl, and —Se—(CH₂)_(m)—R61, m andR61 being defined above.

The terms triflyl, tosyl, mesyl, and nonaflyl are art-recognized andrefer to trifluoromethanesulfonyl, p-toluenesulfonyl, methanesulfonyl,and nonafluorobutanesulfonyl groups, respectively. The terms triflate,tosylate, mesylate, and nonaflate are art-recognized and refer totrifluoromethanesulfonate ester, p-toluenesulfonate ester,methanesulfonate ester, and nonafluorobutanesulfonate ester functionalgroups and molecules that contain said groups, respectively.

The abbreviations Me, Et, Ph, Tf, Nf, Ts, and Ms represent methyl,ethyl, phenyl, trifluoromethanesulfonyl, nonafluorobutanesulfonyl,p-toluenesulfonyl and methanesulfonyl, respectively. A morecomprehensive list of the abbreviations utilized by organic chemists ofordinary skill in the art appears in the first issue of each volume ofthe Journal of Organic Chemistry; this list is typically presented in atable entitled Standard List of Abbreviations.

Certain compounds contained in compositions of the present invention mayexist in particular geometric or stereoisomeric forms. In addition,polymers of the present invention may also be optically active. Thepresent invention contemplates all such compounds, including cis- andtrans-isomers, R- and S-enantiomers, diastereomers, (D)-isomers,(L)-isomers, the racemic mixtures thereof, and other mixtures thereof,as falling within the scope of the invention. Additional asymmetriccarbon atoms may be present in a substituent such as an alkyl group. Allsuch isomers, as well as mixtures thereof, are intended to be includedin this invention.

If, for instance, a particular enantiomer of compound of the presentinvention is desired, it may be prepared by asymmetric synthesis, or byderivation with a chiral auxiliary, where the resulting diastereomericmixture is separated and the auxiliary group cleaved to provide the puredesired enantiomers. Alternatively, where the molecule contains a basicfunctional group, such as amino, or an acidic functional group, such ascarboxyl, diastereomeric salts are formed with an appropriateoptically-active acid or base, followed by resolution of thediastereomers thus formed by fractional crystallization orchromatographic means well known in the art, and subsequent recovery ofthe pure enantiomers.

It will be understood that “substitution” or “substituted with” includesthe implicit proviso that such substitution is in accordance withpermitted valence of the substituted atom and the substituent, and thatthe substitution results in a stable compound, e.g., which does notspontaneously undergo transformation such as by rearrangement,cyclization, elimination, or other reaction.

The term “substituted” is also contemplated to include all permissiblesubstituents of organic compounds. In a broad aspect, the permissiblesubstituents include acyclic and cyclic, branched and unbranched,carbocyclic and heterocyclic, aromatic and nonaromatic substituents oforganic compounds. Illustrative substituents include, for example, thosedescribed herein above. The permissible substituents may be one or moreand the same or different for appropriate organic compounds. Forpurposes of this invention, the heteroatoms such as nitrogen may havehydrogen substituents and/or any permissible substituents of organiccompounds described herein which satisfy the valences of theheteroatoms. This invention is not intended to be limited in any mannerby the permissible substituents of organic compounds.

The phrase “protecting group” as used herein means temporarysubstituents which protect a potentially reactive functional group fromundesired chemical transformations. Examples of such protecting groupsinclude esters of carboxylic acids, silyl ethers of alcohols, andacetals and ketals of aldehydes and ketones, respectively. The field ofprotecting group chemistry has been reviewed (Greene, T. W.; Wuts,P.G.M. Protective Groups in Organic Synthesis, 2^(nd) ed.; Wiley: NewYork, 1991). Protected forms of the inventive compounds are includedwithin the scope of this invention.

For purposes of this invention, the chemical elements are identified inaccordance with the Periodic Table of the Elements, CAS version,Handbook of Chemistry and Physics, 67th Ed., 1986-87, inside cover.

Compositions of the Invention

Methanofullerenes

One aspect of the present invention relates to a composition comprisinga compound of formula I and a compound of formula II, wherein formula Iis represented by:

wherein

n is 1 or 2;

A is a C₆₀ fullerene bonded to —C(X)(Y)— via a methano-bridge;

X is optionally substituted aryl or aralkyl; and

Y is an optionally substituted alkyl, optionally substituted cycloalkyl,optionally substituted heteroalkyl, optionally substitutedheterocycloalkyl, optionally substituted alkenyl, or optionallysubstituted aralkyl; and

formula II is represented by:

wherein

n is 1 or 2;

A′ is a C₇₀ fullerene bonded to —C(X)(Y)— via a methano-bridge;

X′ is optionally substituted aryl or optionally substituted aralkyl; and

Y′ is optionally substituted alkyl, optionally substituted cycloalkyl,optionally substituted heteroalkyl, optionally substitutedheterocycloalkyl, optionally substituted alkenyl, or optionallysubstituted aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is aryl or aralkyl, each of whichis optionally substituted with one or more of halogen, hydroxyl, alkyl,alkoxyl, alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹;wherein R¹ represents independently for each occurrence H, alkyl, aryl,or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is aryl or aralkyl, each of whichis optionally substituted with one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is optionally substituted aryl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is optionally substituted phenylor thiophenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is optionally substitutedthiophenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is phenyl optionally substitutedwith one or more of halogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(R¹)₂,—C(O)R¹, —OC(O)R₁, —CO₂R¹, or —N(R¹)C(O)R¹; wherein R¹ representsindependently for each occurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is phenyl optionally substitutedwith one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is phenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is alkyl, cycloalkyl, heteroalkyl,heterocycloalkyl, alkenyl, or aralkyl, each of which is optionallysubstituted with one or more of halogen, hydroxyl, alkyl, alkoxyl,alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹; wherein R¹represents independently for each occurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is alkyl, cycloalkyl, orheteroalkyl, each of which is optionally substituted with one or more ofhalogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹,—CO₂R¹, or —N(R¹)C(O)R¹; wherein R¹ represents independently for eachoccurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is alkyl optionally substitutedwith one or more of —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹; whereinR¹ represents independently for each occurrence H, alkyl, aryl, oraralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is C1-C6 alkyl substituted withone or more of —C(O)R¹, —OC(O)R¹, or —CO₂R¹; wherein R¹ representsindependently for each occurrence alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is C1-C6 alkyl substituted with a—C(O)R¹, —OC(O)R¹, or —CO₂R¹; wherein R¹ represents independently foreach occurrence alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is C1-C6 alkyl substituted with a—CO₂R¹; wherein R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is —(CH₂)_(n)—CO₂R¹, n is aninteger in the range of 1-6, and R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is optionally substituted aryl,and Y is optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is optionally substituted phenylor thiophenyl, and Y is C1-C6 alkyl substituted with a —CO₂R¹; whereinR¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is optionally substitutedthiophenyl, and Y is C1-C6 alkyl substituted with a —CO₂R¹; wherein R¹is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is phenyl and Y is —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is aryl or aralkyl, each of whichis optionally substituted with one or more of halogen, hydroxyl, alkyl,alkoxyl, alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹;wherein R¹ represents independently for each occurrence H, alkyl, aryl,or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is aryl or aralkyl, each of whichis optionally substituted with one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is optionally substituted aryl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is optionally substituted phenylor thiophenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is optionally substitutedthiophenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is phenyl optionally substitutedwith one or more of halogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(R¹)₂,—C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹; wherein R¹ representsindependently for each occurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is phenyl optionally substitutedwith one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is phenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is alkyl, cycloalkyl,heteroalkyl, heterocycloalkyl, alkenyl, or aralkyl, each of which isoptionally substituted with one or more of halogen, hydroxyl, alkyl,alkoxyl, alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹;wherein R¹ represents independently for each occurrence H, alkyl, aryl,or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is alkyl, cycloalkyl, orheteroalkyl, each of which is optionally substituted with one or more ofhalogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹,—CO₂R¹, or —N(R¹)C(O)R¹; wherein R¹ represents independently for eachoccurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is alkyl optionally substitutedwith one or more of —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹; whereinR¹ represents independently for each occurrence H, alkyl, aryl, oraralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is C1-C6 alkyl substituted withone or more of —C(O)R¹, —OC(O)R¹, or —CO₂R¹; wherein R¹ representsindependently for each occurrence alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is C1-C6 alkyl substituted with a—C(O)R¹, —OC(O)R¹, or —CO₂R¹; wherein R¹ represents independently foreach occurrence alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is C1-C6 alkyl substituted with a—CO₂R¹; wherein R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is —(CH₂)_(n)—CO₂R¹, n is aninteger in the range of 1-6, and R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is optionally substituted aryl,and Y′ is optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is optionally substituted phenylor thiophenyl, and Y′ is C1-C6 alkyl substituted with a —CO₂R¹; whereinR¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is optionally substitutedthiophenyl, and Y′ is C1-C6 alkyl substituted with a —CO₂R¹; wherein R¹is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is phenyl and Y′ is—(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X and X′ are optionally substitutedaryl, and Y and Y′ are optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X and X′ are optionally substitutedphenyl or thiophenyl, and Y and Y′ are C1-C6 alkyl substituted with a—CO₂R¹; wherein R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X and X′ are optionally substitutedthiophenyl, and Y and Y′ are C1-C6 alkyl substituted with a —CO₂R¹;wherein R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X and X′ are phenyl, and Y and Y′are —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein the ratio of the weight percentageof said compound of Formula I to said compound of Formula II is in therange of about 3:1 to about 1:3.

In certain embodiments, the present invention relates to theaforementioned composition, wherein the ratio of the weight percentageof said compound of Formula I to said compound of Formula II is in therange of about 3:1 to about 1:1.

In certain embodiments, the present invention relates to theaforementioned composition, wherein the ratio of the weight percentageof said compound of Formula I to said compound of Formula II is about2:1.

In certain embodiments, the present invention relates to theaforementioned composition, wherein said compound of Formula I comprisesabout 50 wt % to about 75 wt % of said composition, and said compound ofFormula II comprises about 25 wt % to about 50 wt % of said compositionsuch that the sum of the weight percent of said compound of Formula Iand said compound of Formula II equals greater than about 99 wt % ofsaid composition.

In certain embodiments, the present invention relates to theaforementioned composition, wherein said compound of Formula I comprisesabout 60 wt % to about 70 wt % of said composition, and said compound ofFormula II comprises about 30 wt % to about 40 wt % of said compositionsuch that the sum of the weight percent of said compound of Formula Iand said compound of Formula II equals greater than about 99 wt % ofsaid composition.

Another aspect of the present invention relates to a compositionconsisting essentially of a compound of formula I and a compound offormula II, wherein formula I is represented by:

wherein

n is 1 or 2;

A is a C₆₀ fullerene bonded to —C(X)(Y)— via a methano-bridge;

X is optionally substituted aryl or aralkyl; and

Y is optionally substituted alkyl, optionally substituted cycloalkyl,optionally substituted heteroalkyl, optionally substitutedheterocycloalkyl, optionally substituted alkenyl, or optionallysubstituted aralkyl; and

formula II is represented by:

wherein

n is 1 or 2;

A′ is a C₇₀ fullerene bonded to —C(X)(Y)— via a methano-bridge;

X′ is optionally substituted aryl or optionally substituted aralkyl; and

Y′ is optionally substituted alkyl, optionally substituted cycloalkyl,optionally substituted heteroalkyl, optionally substitutedheterocycloalkyl, optionally substituted alkenyl, or optionallysubstituted aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is aryl or aralkyl, each of whichis optionally substituted with one or more of halogen, hydroxyl, alkyl,alkoxyl, alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹;wherein R¹ represents independently for each occurrence H, alkyl, aryl,or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is aryl or aralkyl, each of whichis optionally substituted with one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is optionally substituted aryl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is optionally substituted phenylor thiophenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is optionally substitutedthiophenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is phenyl optionally substitutedwith one or more of halogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(R¹)₂,—C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹; wherein R¹ representsindependently for each occurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is phenyl optionally substitutedwith one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is phenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is alkyl, cycloalkyl, heteroalkyl,heterocycloalkyl, alkenyl, or aralkyl, each of which is optionallysubstituted with one or more of halogen, hydroxyl, alkyl, alkoxyl,alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹; wherein R¹represents independently for each occurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is alkyl, cycloalkyl, orheteroalkyl, each of which is optionally substituted with one or more ofhalogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹,—CO₂R¹, or —N(R¹)C(O)R¹; wherein R¹ represents independently for eachoccurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is alkyl optionally substitutedwith one or more of —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹; whereinR¹ represents independently for each occurrence H, alkyl, aryl, oraralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is C1-C6 alkyl substituted withone or more of —C(O)R¹, —OC(O)R¹, or —CO₂R¹; wherein R¹ representsindependently for each occurrence alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is C1-C6 alkyl substituted with a—C(O)R¹, —OC(O)R¹, or —CO₂R¹; wherein R¹ represents independently foreach occurrence alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is C1-C6 alkyl substituted with a—CO₂R¹; wherein R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is —(CH₂)_(n)—CO₂R¹, n is aninteger in the range of 1-6, and R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is optionally substituted aryl,and Y is optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is optionally substituted phenylor thiophenyl, and Y is C1-C6 alkyl substituted with a —CO₂R¹; whereinR¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is optionally substitutedthiophenyl, and Y is C1-C6 alkyl substituted with a —CO₂R¹; wherein R¹is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is phenyl and Y is —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is aryl or aralkyl, each of whichis optionally substituted with one or more of halogen, hydroxyl, alkyl,alkoxyl, alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹;wherein R¹ represents independently for each occurrence H, alkyl, aryl,or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is aryl or aralkyl, each of whichis optionally substituted with one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is optionally substituted aryl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is optionally substituted phenylor thiophenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is optionally substitutedthiophenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is phenyl optionally substitutedwith one or more of halogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(R¹)₂,—C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹; wherein R¹ representsindependently for each occurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is phenyl optionally substitutedwith one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is phenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is alkyl, cycloalkyl,heteroalkyl, heterocycloalkyl, alkenyl, or aralkyl, each of which isoptionally substituted with one or more of halogen, hydroxyl, alkyl,alkoxyl, alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹;wherein R¹ represents independently for each occurrence H, alkyl, aryl,or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is alkyl, cycloalkyl, orheteroalkyl, each of which is optionally substituted with one or more ofhalogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹,—CO₂R¹, or —N(R¹)C(O)R¹; wherein R¹ represents independently for eachoccurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is alkyl optionally substitutedwith one or more of —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹; whereinR¹ represents independently for each occurrence H, alkyl, aryl, oraralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is C1-C6 alkyl substituted withone or more of —C(O)R¹, —OC(O)R¹, or —CO₂R¹; wherein R¹ representsindependently for each occurrence alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is C1-C6 alkyl substituted with a—C(O)R¹, —OC(O)R¹, or —CO₂R¹; wherein R¹ represents independently foreach occurrence alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is C1-C6 alkyl substituted with a—CO₂R¹; wherein R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is —(CH₂)_(n)—CO₂R¹, n is aninteger in the range of 1-6, and R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is optionally substituted aryl,and Y′ is optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is optionally substituted phenylor thiophenyl, and Y′ is C1-C6 alkyl substituted with a —CO₂R¹; whereinR¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is optionally substitutedthiophenyl, and Y′ is C1-C6 alkyl substituted with a —CO₂R¹; wherein R¹is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is phenyl and Y′ is—(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X and X′ are optionally substitutedaryl, and Y and Y′ are optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X and X′ are optionally substitutedphenyl or thiophenyl, and Y and Y′ are C1-C6 alkyl substituted with a—CO₂R¹; wherein R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X and X′ are optionally substitutedthiophenyl, and Y and Y′ are C1-C6 alkyl substituted with a —CO₂R¹;wherein R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X and X′ are phenyl, and Y and Y′are —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein the ratio of the weight percentageof said compound of Formula I to said compound of Formula II is in therange of about 3:1 to about 1:3.

In certain embodiments, the present invention relates to theaforementioned composition, wherein the ratio of the weight percentageof said compound of Formula I to said compound of Formula II is in therange of about 3:1 to about 1:1.

In certain embodiments, the present invention relates to theaforementioned composition, wherein the ratio of the weight percentageof said compound of Formula I to said compound of Formula II is about2:1.

In certain embodiments, the present invention relates to theaforementioned composition, wherein said compound of Formula I comprisesabout 50 wt % to about 75 wt % of said composition, and said compound ofFormula II comprises about 25 wt % to about 50 wt % of said compositionsuch that the sum of the weight percent of said compound of Formula Iand said compound of Formula II equals greater than about 99 wt % ofsaid composition.

In certain embodiments, the present invention relates to theaforementioned composition, wherein said compound of Formula I comprisesabout 60 wt % to about 70 wt % of said composition, and said compound ofFormula II comprises about 30 wt % to about 40 wt % of said compositionsuch that the sum of the weight percent of said compound of Formula Iand said compound of Formula II equals greater than about 99 wt % ofsaid composition.

Prato Derivatives

In certain embodiments, the invention refers to a composition comprisinga compound of formula III, and a compound of formula IV, wherein formulaIII is represented by:

wherein

n is 1 or 2;

A is a C₆₀ fullerene bonded to —C(R₄R₅)—N(R₃)—C(R₁R₂)—;

R₁ is optionally substituted aryl or aralkyl; and

R₂, R₃, R₄, and R₅ are optionally substituted alkyl, optionallysubstituted cycloalkyl, optionally substituted heteroalkyl, optionallysubstituted heterocycloalkyl, optionally substituted alkenyl, oroptionally substituted aralkyl; and

formula IV is represented by:

wherein

n is 1 or 2;

A′ is a C₇₀ fullerene bonded to —C(R₄R₅)—N(R₃)—C(R₁R₂)—;

R₁′ is optionally substituted aryl or optionally substituted aralkyl;and

R₂′, R₃′, R₄′, and R₅′ are optionally substituted alkyl, optionallysubstituted cycloalkyl, optionally substituted heteroalkyl, optionallysubstituted heterocycloalkyl, optionally substituted alkenyl, oroptionally substituted aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ is aryl or aralkyl, each of whichis optionally substituted with one or more of halogen, hydroxyl, alkyl,alkoxyl, alkenyl, —N(X¹)₂, —C(O)X¹, —OC(O)X¹, —CO₂X¹, or —N(X¹)C(O)X¹;wherein X¹ represents independently for each occurrence H, alkyl, aryl,or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ is aryl or aralkyl, each of whichis optionally substituted with one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ is optionally substituted aryl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ is optionally substituted phenylor thiophenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ is phenyl optionally substitutedwith one or more of halogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(X¹)₂,—C(O)X¹, —OC(O)X¹, —CO₂X¹, or —N(X¹)C(O)X¹; wherein X¹ representsindependently for each occurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ is phenyl optionally substitutedwith one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ is phenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂, R₃, R₄, and/or R₅ are alkyl,cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, or aralkyl, each ofwhich is optionally substituted with one or more of halogen, hydroxyl,alkyl, alkoxyl, alkenyl, —N(X¹)₂, —C(O)X¹, —OC(O)X¹, —CO₂X¹, or—N(X¹)C(O)X¹; wherein X¹ represents independently for each occurrence H,alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂, R₃, R₄, and/or R₅ are alkyl,cycloalkyl, or heteroalkyl, each of which is optionally substituted withone or more of halogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(X¹)₂,—C(O)X¹, —OC(O)X¹, —CO₂X¹, or —N(X¹)C(O)X¹; wherein X¹ representsindependently for each occurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂, R₃, R₄, and/or R₅ are optionallysubstituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂, R₃, R₄, and/or R₅ are alkyloptionally substituted with one or more of —C(O)X¹, —OC(O)X¹, —CO₂X¹, or—N(X¹)C(O)X¹; wherein X¹ represents independently for each occurrence H,alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂, R₃, R₄, and/or R₅ are C1-C6alkyl substituted with one or more of —C(O)X¹, —OC(O)X¹, or —CO₂X¹;wherein X¹ represents independently for each occurrence alkyl, aryl, oraralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂, R₃, R₄, and/or R₅ are C1-C6alkyl substituted with a —C(O)X¹, —OC(O)X¹, or —CO₂X¹; wherein X¹represents independently for each occurrence alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂, R₃, R₄, and/or R₅ are C1-C6alkyl substituted with a —CO₂X¹; wherein X¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂, R₃, R₄, and/or R₅ are—(CH₂)_(n)—CO₂X¹, n is an integer in the range of 1-6, and X¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂, R₃, R₄, and/or R₅ are—(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ is optionally substituted aryl,and R₂, R₃, R₄, and/or R₅ are optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ is optionally substituted phenylor thiophenyl, and R₂, R₃, R₄, and/or R₅ are C1-C6 alkyl substitutedwith a —CO₂X¹; wherein X¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ is phenyl and R₂, R₃, R₄, and/orR₅ are —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁′ is aryl or aralkyl, each ofwhich is optionally substituted with one or more of halogen, hydroxyl,alkyl, alkoxyl, alkenyl, —N(X¹)₂, —C(O)X¹, —OC(O)X¹, —CO₂X¹, or—N(X¹)C(O)X¹; wherein X¹ represents independently for each occurrence H,alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁′ is aryl or aralkyl, each ofwhich is optionally substituted with one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁′ is optionally substituted aryl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁′ is optionally substituted phenylor thiophenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁′ is phenyl optionally substitutedwith one or more of halogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(X¹)₂,—C(O)X¹, —OC(O)X¹, —CO₂X¹, or —N(X¹)C(O)X¹; wherein X¹ representsindependently for each occurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁′ is phenyl optionally substitutedwith one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁′ is phenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂′, R₃′, R₄′, and/or R₅′ are alkyl,cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, or aralkyl, each ofwhich is optionally substituted with one or more of halogen, hydroxyl,alkyl, alkoxyl, alkenyl, —N(X¹)₂, —C(O)X¹, —OC(O)X¹, —CO₂X¹, or—N(X¹)C(O)X¹; wherein X¹ represents independently for each occurrence H,alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂′, R₃′, R₄′, and/or R₅′ are alkyl,cycloalkyl, or heteroalkyl, each of which is optionally substituted withone or more of halogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(X¹)₂,—C(O)X¹, —OC(O)X¹, —CO₂X¹, or —N(X¹)C(O)X¹; wherein X¹ representsindependently for each occurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂′, R₃′, R₄′, and/or R₅′ areoptionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂′, R₃′, R₄′, and/or R₅′ are alkyloptionally substituted with one or more of —C(O)X¹, —OC(O)X¹, —CO₂X¹, or—N(X¹)C(O)X¹; wherein X¹ represents independently for each occurrence H,alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂′, R₃′, R₄′, and/or R₅′ are C1-C6alkyl substituted with one or more of —C(O)X¹, —OC(O)X¹, or —CO₂X¹;wherein X¹ represents independently for each occurrence alkyl, aryl, oraralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂′, R₃′, R₄′, and/or R₅′ are C1-C6alkyl substituted with a —C(O)X¹, —OC(O)X¹, or —CO₂X¹; wherein X¹represents independently for each occurrence alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂′, R₃′, R₄′, and/or R₅′ are C1-C6alkyl substituted with a —CO₂X¹; wherein X¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂′, R₃′, R₄′, and/or R₅′ are—(CH₂)_(n)—CO₂X¹, n is an integer in the range of 1-6, and X¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂′, R₃′, R₄′, and/or R₅′ are—(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁′ is optionally substituted aryl,and R₂′, R₃′, R₄′, and/or R₅′ are optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁′ is optionally substituted phenylor thiophenyl, and R₂′, R₃′, R₄′, and/or R₅′ are C₁-C₆ alkyl substitutedwith a —CO₂X¹; wherein X¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁′ is phenyl; and R₂′, R₃′, R₄′,and/or R₅′ are —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ and R₁′ are optionallysubstituted aryl, and R₂, R₃, R₄, and/or R₅ and R₂′, R₃′, R₄′, and/orR₅′ are optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ and R₁′ are optionallysubstituted phenyl or thiophenyl, and R₂, R₃, R₄, and/or R₅ and R₂′,R₃′, R₄′, and/or R₅′ are C1-C6 alkyl substituted with a —CO₂X¹; whereinX¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ and R₁′ are phenyl, and R₂, R₃,R₄, and/or R₅ and R₂′, R₃′, R₄′, and/or R₅′ are —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein the ratio of the weight percentageof said compound of Formula III to said compound of Formula IV is in therange of about 3:1 to about 1:3.

In certain embodiments, the present invention relates to theaforementioned composition, wherein the ratio of the weight percentageof said compound of Formula III to said compound of Formula IV is in therange of about 3:1 to about 1:1.

In certain embodiments, the present invention relates to theaforementioned composition, wherein the ratio of the weight percentageof said compound of Formula III to said compound of Formula IV is about2:1.

In certain embodiments, the present invention relates to theaforementioned composition, wherein said compound of Formula IIIcomprises about 5 wt % to about 95 wt % of said composition, and saidcompound of Formula IV comprises about 5 wt % to about 95 wt % of saidcomposition such that the sum of the weight percent of said compound ofFormula III and said compound of Formula IV equals greater than about 99wt % of said composition.

In certain embodiments, the present invention relates to theaforementioned composition, wherein said compound of Formula IIIcomprises about 5 wt % to about 95 wt % of said composition, and saidcompound of Formula IV comprises about 5 wt % to about 95 wt % of saidcomposition such that the sum of the weight percent of said compound ofFormula III and said compound of Formula IV equals greater than about 99wt % of said composition.

In certain embodiments, the present invention relates to a composition,consisting essentially of a compound of formula III, and a compound offormula IV, wherein formula III is represented by:

wherein

n is 1 for the mono-adduct and n is 2 for the bis-adduct;

A is a C₆₀ fullerene bonded to —C(R₄R₅)—N(R₃)—C(R¹R₂)—;

R₁ is optionally substituted aryl or aralkyl; and

R₂, R₃, R₄, and R₅ are optionally substituted alkyl, optionallysubstituted cycloalkyl, optionally substituted heteroalkyl, optionallysubstituted heterocycloalkyl, optionally substituted alkenyl, oroptionally substituted aralkyl; and

formula IV is represented by:

wherein

n is 1 for the mono-adduct and n is 2 for the bis-adduct;

A′ is a C₇₀ fullerene bonded to —C(R₄R₅)—N(R₃)—C(R₁R₂)—;

R₁′ is optionally substituted aryl or optionally substituted aralkyl;and

R₂′, R₃′, R₄′, and R₅′ are optionally substituted alkyl, optionallysubstituted cycloalkyl, optionally substituted heteroalkyl, optionallysubstituted heterocycloalkyl, optionally substituted alkenyl, oroptionally substituted aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ is aryl or aralkyl, each of whichis optionally substituted with one or more of halogen, hydroxyl, alkyl,alkoxyl, alkenyl, —N(X¹)₂, —C(O)X¹, —OC(O)X¹, —CO₂X¹, or —N(X¹)C(O)X¹;wherein X¹ represents independently for each occurrence H, alkyl, aryl,or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ is aryl or aralkyl, each of whichis optionally substituted with one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ is optionally substituted aryl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ is optionally substituted phenylor thiophenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ is phenyl optionally substitutedwith one or more of halogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(X¹)₂,—C(O)X¹, —OC(O)X¹, —CO₂X¹, or —N(X¹)C(O)X¹; wherein X¹ representsindependently for each occurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ is phenyl optionally substitutedwith one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ is phenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂, R₃, R₄, and/or R₅ are alkyl,cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, or aralkyl, each ofwhich is optionally substituted with one or more of halogen, hydroxyl,alkyl, alkoxyl, alkenyl, —N(X¹)₂, —C(O)X¹, —OC(O)X¹, —CO₂X¹, or—N(X¹)C(O)X¹; wherein X¹ represents independently for each occurrence H,alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂, R³, R₄, and/or R₅ are alkyl,cycloalkyl, or heteroalkyl, each of which is optionally substituted withone or more of halogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(X¹)₂,—C(O)X¹, —OC(O)X¹, —CO₂X¹, or —N(X¹)C(O)X¹; wherein X¹ representsindependently for each occurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂, R₃, R₄, and/or R₅ are optionallysubstituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂, R₃, R₄, and/or R₅ are alkyloptionally substituted with one or more of —C(O)X¹, —OC(O)X¹, —CO₂X¹, or—N(X¹)C(O)X¹; wherein X¹ represents independently for each occurrence H,alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂, R₃, R₄, and/or R₅ are C1-C6alkyl substituted with one or more of —C(O)X¹, —OC(O)X¹, or —CO₂X¹;wherein X¹ represents independently for each occurrence alkyl, aryl, oraralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂, R₃, R₄, and/or R₅ are C1-C6alkyl substituted with a —C(O)X¹, —OC(O)X¹, or —CO₂X¹; wherein X¹represents independently for each occurrence alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂, R₃, R₄, and/or R₅ are C1-C6alkyl substituted with a —CO₂X¹; wherein X¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂, R₃, R₄, and/or R₅ are—(CH₂)_(n)—CO₂X¹, n is an integer in the range of 1-6, and X¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂, R₃, R₄, and/or R₅ are—(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ is optionally substituted aryl,and R₂, R₃, R₄, and/or R₅ are optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ is optionally substituted phenylor thiophenyl, and R₂, R₃, R₄, and/or R₅ are C1-C6 alkyl substitutedwith a —CO₂X¹; wherein X¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ is phenyl and R₂, R₃, R₄, and/orR₅ are —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁′ is aryl or aralkyl, each ofwhich is optionally substituted with one or more of halogen, hydroxyl,alkyl, alkoxyl, alkenyl, —N(X¹)₂, —C(O)X¹, —OC(O)X¹, —CO₂X¹, or—N(X¹)C(O)X¹; wherein X¹ represents independently for each occurrence H,alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁′ is aryl or aralkyl, each ofwhich is optionally substituted with one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁′ is optionally substituted aryl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁′ is optionally substituted phenylor thiophenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁′ is phenyl optionally substitutedwith one or more of halogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(X¹)₂,—C(O)X¹, —OC(O)X¹, —CO₂X¹, or —N(X¹)C(O)X¹; wherein X¹ representsindependently for each occurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁′ is phenyl optionally substitutedwith one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁′ is phenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂′, R₃′, R₄′, and/or R₅′ are alkyl,cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, or aralkyl, each ofwhich is optionally substituted with one or more of halogen, hydroxyl,alkyl, alkoxyl, alkenyl, —N(X¹)₂, —C(O)X¹, —OC(O)X¹, —CO₂X¹, or—N(X¹)C(O)X¹; wherein X¹ represents independently for each occurrence H,alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂′, R₃′, R₄′, and/or R₅′ are alkyl,cycloalkyl, or heteroalkyl, each of which is optionally substituted withone or more of halogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(X¹)₂,—C(O)X¹, —OC(O)X¹, —CO₂X¹, or —N(X¹)C(O)X¹; wherein X¹ representsindependently for each occurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂′, R₃′, R₄′, and/or R₅′ areoptionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂′, R₃′, R₄′, and/or R₅′ are alkyloptionally substituted with one or more of —C(O)X¹, —OC(O)X¹, —CO₂X¹, or—N(X¹)C(O)X¹; wherein X¹ represents independently for each occurrence H,alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂′, R₃′, R₄′, and/or R₅′ are C1-C6alkyl substituted with one or more of —C(O)X¹, —OC(O)X¹, or —CO₂X¹;wherein X¹ represents independently for each occurrence alkyl, aryl, oraralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂′, R₃′, R₄′, and/or R₅′ are C1-C6alkyl substituted with a —C(O)X¹, —OC(O)X¹, or —CO₂X¹; wherein X¹represents independently for each occurrence alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂′, R₃′, R₄′, and/or R₅′ are C1-C6alkyl substituted with a —CO₂X¹; wherein X¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂′, R₃′, R₄′, and/or R₅′ are—(CH₂)_(n)—CO₂X¹, n is an integer in the range of 1-6, and X¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₂′, R₃′, R₄′, and/or R₅′ are—(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁′ is optionally substituted aryl,and R₂′, R₃′, R₄′, and/or R₅′ are optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁′ is optionally substituted phenylor thiophenyl, and R₂′, R₃′, R₄′, and/or R₅′ are C₁-C₆ alkyl substitutedwith a —CO₂X¹; wherein X¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁′ is phenyl and R₂′, R₃′, R₄′,and/or R₅′ are —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ and R₁′ are optionallysubstituted aryl, and R₂, R₃, R₄, and/or R₅ and R₂′, R₃′, R₄′, and/orR₅′ are optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ and R₁′ are optionallysubstituted phenyl or thiophenyl, and R₂, R₃, R₄, and/or R₅ and R₂′,R₃′, R₄′, and/or R₅′ are C1-C6 alkyl substituted with a —CO₂X¹; whereinX¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein R₁ and R₁′ are phenyl, and R₂, R₃,R₄, and/or R₅ and R₂′, R₃′, R₄′, and/or R₅′ are —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein the ratio of the weight percentageof said compound of Formula III to said compound of Formula IV is in therange of about 3:1 to about 1:3.

In certain embodiments, the present invention relates to theaforementioned composition, wherein the ratio of the weight percentageof said compound of Formula III to said compound of Formula IV is in therange of about 3:1 to about 1:1.

In certain embodiments, the present invention relates to theaforementioned composition, wherein the ratio of the weight percentageof said compound of Formula III to said compound of Formula IV is about2:1.

In certain embodiments, the present invention relates to theaforementioned composition, wherein said compound of Formula IIIcomprises about 5 wt % to about 95 wt % of said composition, and saidcompound of Formula IV comprises about 5 wt % to about 95 wt % of saidcomposition such that the sum of the weight percent of said compound ofFormula III and said compound of Formula IV equals greater than about 99wt % of said composition.

In certain embodiments, the present invention relates to theaforementioned composition, wherein said compound of Formula IIIcomprises about 5 wt % to about 95 wt % of said composition, and saidcompound of Formula IV comprises about 5 wt % to about 95 wt % of saidcomposition such that the sum of the weight percent of said compound ofFormula III and said compound of Formula IV equals greater than about 99wt % of said composition.

Bis-Derivatives

In certain embodiments, the present invention relates to a composition,comprising a compound of formula V, and a compound of formula VI,wherein formula V is represented by:

wherein

A is a C₆₀ fullerene bonded to —C(X)(Y)— via a methano-bridge;

X is optionally substituted aryl or aralkyl; and

Y is an optionally substituted alkyl, optionally substituted cycloalkyl,optionally substituted heteroalkyl, optionally substitutedheterocycloalkyl, optionally substituted alkenyl, or optionallysubstituted aralkyl; and formula VI is represented by:

wherein

A′ is a C₇₀ fullerene bonded to —C(X)(Y)— via a methano-bridge;

X′ is optionally substituted aryl or optionally substituted aralkyl; and

Y′ is optionally substituted alkyl, optionally substituted cycloalkyl,optionally substituted heteroalkyl, optionally substitutedheterocycloalkyl, optionally substituted alkenyl, or optionallysubstituted aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is aryl or aralkyl, each of whichis optionally substituted with one or more of halogen, hydroxyl, alkyl,alkoxyl, alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹;wherein R¹ represents independently for each occurrence H, alkyl, aryl,or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is aryl or aralkyl, each of whichis optionally substituted with one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is optionally substituted aryl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is optionally substituted phenylor thiophenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is phenyl optionally substitutedwith one or more of halogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(R¹)₂,—C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹; wherein R¹ representsindependently for each occurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is phenyl optionally substitutedwith one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is phenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is alkyl, cycloalkyl, heteroalkyl,heterocycloalkyl, alkenyl, or aralkyl, each of which is optionallysubstituted with one or more of halogen, hydroxyl, alkyl, alkoxyl,alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹; wherein R¹represents independently for each occurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is alkyl, cycloalkyl, orheteroalkyl, each of which is optionally substituted with one or more ofhalogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹,—CO₂R¹, or —N(R¹)C(O)R¹; wherein R¹ represents independently for eachoccurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is alkyl optionally substitutedwith one or more of —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹; whereinR¹ represents independently for each occurrence H, alkyl, aryl, oraralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is C1-C6 alkyl substituted withone or more of —C(O)R¹, —OC(O)R¹, or —CO₂R¹; wherein R¹ representsindependently for each occurrence alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is C1-C6 alkyl substituted with a—C(O)R¹, —OC(O)R¹, or —CO₂R¹; wherein R¹ represents independently foreach occurrence alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is C1-C6 alkyl substituted with a—CO₂R¹; wherein R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is —(CH₂)_(n)—CO₂R¹, n is aninteger in the range of 1-6, and R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is optionally substituted aryl,and Y is optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is optionally substituted phenylor thiophenyl, and Y is C1-C6 alkyl substituted with a —CO₂R¹; whereinR¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is phenyl and Y is —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is aryl or aralkyl, each of whichis optionally substituted with one or more of halogen, hydroxyl, alkyl,alkoxyl, alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹;wherein R¹ represents independently for each occurrence H, alkyl, aryl,or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is aryl or aralkyl, each of whichis optionally substituted with one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is optionally substituted aryl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is optionally substituted phenylor thiophenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is phenyl optionally substitutedwith one or more of halogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(R¹)₂,—C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹; wherein R¹ representsindependently for each occurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is phenyl optionally substitutedwith one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is phenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is alkyl, cycloalkyl,heteroalkyl, heterocycloalkyl, alkenyl, or aralkyl, each of which isoptionally substituted with one or more of halogen, hydroxyl, alkyl,alkoxyl, alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹;wherein R¹ represents independently for each occurrence H, alkyl, aryl,or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is alkyl, cycloalkyl, orheteroalkyl, each of which is optionally substituted with one or more ofhalogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹,—CO₂R¹, or —N(R¹)C(O)R¹; wherein R¹ represents independently for eachoccurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is alkyl optionally substitutedwith one or more of —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹; whereinR¹ represents independently for each occurrence H, alkyl, aryl, oraralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is C1-C6 alkyl substituted withone or more of —C(O)R¹, —OC(O)R¹, or —CO₂R¹; wherein R¹ representsindependently for each occurrence alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is C1-C6 alkyl substituted with a—C(O)R¹, —OC(O)R¹, or —CO₂R¹; wherein R¹ represents independently foreach occurrence alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is C1-C6 alkyl substituted with a—CO₂R¹; wherein R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is —(CH₂)_(n)—CO₂R¹, n is aninteger in the range of 1-6, and R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is optionally substituted aryl,and Y′ is optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is optionally substituted phenylor thiophenyl, and Y′ is C1-C6 alkyl substituted with a —CO₂R¹; whereinR¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is phenyl and Y′ is—(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X and X′ are optionally substitutedaryl, and Y and Y′ are optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X and X′ are optionally substitutedphenyl or thiophenyl, and Y and Y′ are C1-C6 alkyl substituted with a—CO₂R¹; wherein R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X and X′ are phenyl, and Y and Y′are —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein the ratio of the weight percentageof said compound of Formula V to said compound of Formula VI is in therange of about 3:1 to about 1:3.

In certain embodiments, the present invention relates to theaforementioned composition, wherein the ratio of the weight percentageof said compound of Formula V to said compound of Formula VI is in therange of about 3:1 to about 1:1.

In certain embodiments, the present invention relates to theaforementioned composition, wherein the ratio of the weight percentageof said compound of Formula V to said compound of Formula VI is about2:1.

In certain embodiments, the present invention relates to theaforementioned composition, wherein said compound of Formula V comprisesabout 5 wt % to about 95 wt % of said composition, and said compound ofFormula VI comprises about 5 wt % to about 95 wt % of said compositionsuch that the sum of the weight percent of said compound of Formula Vand said compound of Formula VI equals greater than about 99 wt % ofsaid composition.

In certain embodiments, the present invention relates to theaforementioned composition, wherein said compound of Formula V comprisesabout 5 wt % to about 95 wt % of said composition, and said compound ofFormula VI comprises about 5 wt % to about 95 wt % of said compositionsuch that the sum of the weight percent of said compound of Formula Vand said compound of Formula VI equals greater than about 99 wt % ofsaid composition.

In certain embodiments, the present invention relates to a composition,consisting essentially of a compound of formula V, and a compound offormula VI, wherein formula V is represented by:

wherein

A is a C₆₀ fullerene bonded to —C(X)(Y)— via a methano-bridge;

X is optionally substituted aryl or aralkyl; and

Y is optionally substituted alkyl, optionally substituted cycloalkyl,optionally substituted heteroalkyl, optionally substitutedheterocycloalkyl, optionally substituted alkenyl, or optionallysubstituted aralkyl; and

formula II is represented by:

wherein

A′ is a C₇₀ fullerene bonded to —C(X)(Y)— via a methano-bridge;

X′ is optionally substituted aryl or optionally substituted aralkyl; and

Y′ is optionally substituted alkyl, optionally substituted cycloalkyl,optionally substituted heteroalkyl, optionally substitutedheterocycloalkyl, optionally substituted alkenyl, or optionallysubstituted aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is aryl or aralkyl, each of whichis optionally substituted with one or more of halogen, hydroxyl, alkyl,alkoxyl, alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹;wherein R¹ represents independently for each occurrence H, alkyl, aryl,or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is aryl or aralkyl, each of whichis optionally substituted with one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is optionally substituted aryl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is optionally substituted phenylor thiophenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is phenyl optionally substitutedwith one or more of halogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(R¹)₂,—C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹; wherein R¹ representsindependently for each occurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is phenyl optionally substitutedwith one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is phenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is alkyl, cycloalkyl, heteroalkyl,heterocycloalkyl, alkenyl, or aralkyl, each of which is optionallysubstituted with one or more of halogen, hydroxyl, alkyl, alkoxyl,alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹; wherein R¹represents independently for each occurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is alkyl, cycloalkyl, orheteroalkyl, each of which is optionally substituted with one or more ofhalogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹,—CO₂R¹, or —N(R¹)C(O)R¹; wherein R¹ represents independently for eachoccurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is alkyl optionally substitutedwith one or more of —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹; whereinR¹ represents independently for each occurrence H, alkyl, aryl, oraralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is C1-C6 alkyl substituted withone or more of —C(O)R¹, —OC(O)R¹, or —CO₂R¹; wherein R¹ representsindependently for each occurrence alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is C1-C6 alkyl substituted with a—C(O)R¹, —OC(O)R¹, or —CO₂R¹; wherein R¹ represents independently foreach occurrence alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is C1-C6 alkyl substituted with a—CO₂R¹; wherein R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is —(CH₂)_(n)—CO₂R¹, n is aninteger in the range of 1-6, and R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y is —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is optionally substituted aryl,and Y is optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is optionally substituted phenylor thiophenyl, and Y is C1-C6 alkyl substituted with a —CO₂R¹; whereinR¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X is phenyl and Y is —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is aryl or aralkyl, each of whichis optionally substituted with one or more of halogen, hydroxyl, alkyl,alkoxyl, alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹;wherein R¹ represents independently for each occurrence H, alkyl, aryl,or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is aryl or aralkyl, each of whichis optionally substituted with one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is optionally substituted aryl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is optionally substituted phenylor thiophenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is phenyl optionally substitutedwith one or more of halogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(R¹)₂,—C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹; wherein R¹ representsindependently for each occurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is phenyl optionally substitutedwith one or more of halogen or alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is phenyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is alkyl, cycloalkyl,heteroalkyl, heterocycloalkyl, alkenyl, or aralkyl, each of which isoptionally substituted with one or more of halogen, hydroxyl, alkyl,alkoxyl, alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹;wherein R¹ represents independently for each occurrence H, alkyl, aryl,or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is alkyl, cycloalkyl, orheteroalkyl, each of which is optionally substituted with one or more ofhalogen, hydroxyl, alkyl, alkoxyl, alkenyl, —N(R¹)₂, —C(O)R¹, —OC(O)R¹,—CO₂R¹, or —N(R¹)C(O)R¹; wherein R¹ represents independently for eachoccurrence H, alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is alkyl optionally substitutedwith one or more of —C(O)R¹, —OC(O)R¹, —CO₂R¹, or —N(R¹)C(O)R¹; whereinR¹ represents independently for each occurrence H, alkyl, aryl, oraralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is C1-C6 alkyl substituted withone or more of —C(O)R¹, —OC(O)R¹, or —CO₂R¹; wherein R¹ representsindependently for each occurrence alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is C1-C6 alkyl substituted with a—C(O)R¹, —OC(O)R¹, or —CO₂R¹; wherein R¹ represents independently foreach occurrence alkyl, aryl, or aralkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is C1-C6 alkyl substituted with a—CO₂R¹; wherein R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is —(CH₂)_(n)—CO₂R¹, n is aninteger in the range of 1-6, and R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein Y′ is —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is optionally substituted aryl,and Y′ is optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is optionally substituted phenylor thiophenyl, and Y′ is C1-C6 alkyl substituted with a —CO₂R¹; whereinR¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X′ is phenyl and Y′ is—(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X and X′ are optionally substitutedaryl, and Y and Y′ are optionally substituted alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X and X′ are optionally substitutedphenyl or thiophenyl, and Y and Y′ are C1-C6 alkyl substituted with a—CO₂R¹; wherein R¹ is alkyl.

In certain embodiments, the present invention relates to theaforementioned composition, wherein X and X′ are phenyl, and Y and Y′are —(CH₂)₃—CO₂CH₃.

In certain embodiments, the present invention relates to theaforementioned composition, wherein the ratio of the weight percentageof said compound of Formula V to said compound of Formula VI is in therange of about 3:1 to about 1:3.

In certain embodiments, the present invention relates to theaforementioned composition, wherein the ratio of the weight percentageof said compound of Formula V to said compound of Formula VI is in therange of about 3:1 to about 1:1.

In certain embodiments, the present invention relates to theaforementioned composition, wherein the ratio of the weight percentageof said compound of Formula V to said compound of Formula VI is about2:1.

In certain embodiments, the present invention relates to theaforementioned composition, wherein said compound of Formula V comprisesabout 5 wt % to about 95 wt % of said composition, and said compound ofFormula VI comprises about 5 wt % to about 95 wt % of said compositionsuch that the sum of the weight percent of said compound of Formula Vand said compound of Formula VI equals greater than about 99 wt % ofsaid composition.

In certain embodiments, the present invention relates to theaforementioned composition, wherein said compound of Formula V comprisesabout 5 wt % to about 95 wt % of said composition, and said compound ofFormula VI comprises about 5 wt % to about 95 wt % of said compositionsuch that the sum of the weight percent of said compound of Formula Vand said compound of Formula VI equals greater than about 99 wt % ofsaid composition.

Other Bis-Adducts

In certain embodiments, the present invention relates to bis-adducts ofPCBM, bis-adducts of ThCBM, bis-adducts of Prato, bis-adducts of Bingel,bis-adducts of diazoline, bis-adducts of azafulleroid, bis-adducts ofketolactam, and bis-adducts of Diels Alder.

Other Embodiments

In certain embodiments, the present invention relates to theaforementioned compositions, further comprising about 0.0001% to about5% oxides of C₆₀ fullerenes, and/or about 0.0001% to about 5% oxides ofC₇₀ fullerenes, and/or about 0.0001% to about 5% oxides of C₆₀ fullerenederivatives, and/or about 0.0001% to about 5% C₇₀ fullerene derivatives.

In certain embodiments, the present invention relates to theaforementioned compositions, further comprising about 0.001% to about 2%oxides of C₆₀ fullerenes, and/or about 0.001% to about 2% oxides of C₇₀fullerenes, and/or about 0.001% to about 2% oxides of C₆₀ fullerenederivatives, and/or about 0.001% to about 2% C₇₀ fullerene derivatives.

In certain embodiments, the present invention relates to theaforementioned compositions, further comprising about 0.01% to about 1%oxides of C₆₀ fullerenes, and/or about 0.01% to about 1% oxides of C₇₀fullerenes, and/or about 0.01% to about 1% oxides of C₆₀ fullerenederivatives, and/or about 0.01% to about 1% C₇₀ fullerene derivatives.

In certain embodiments, the present invention relates to theaforementioned compositions, further comprising about 0.0001% to about5% dimer compounds of unreacted C₆₀ fullerenes, and/or about 0.0001% toabout 5% dimer compounds of unreacted C₇₀ fullerenes, and/or about0.0001% to about 5% dimer compounds of C₆₀ fullerene derivatives, and/orabout 0.0001% to about 5% dimer compounds of C₇₀ fullerene derivatives.

In certain embodiments, the present invention relates to theaforementioned compositions, further comprising about 0.001% to about 2%dimer compounds of unreacted C₆₀ fullerenes, and/or about 0.001% toabout 2% dimer compounds of unreacted C₇₀ fullerenes, and/or about0.001% to about 2% dimer compounds of C₆₀ fullerene derivatives, and/orabout 0.001% to about 2% dimer compounds of C₇₀ fullerene derivatives.

In certain embodiments, the present invention relates to theaforementioned compositions, further comprising about 0.001% to about 1%dimer compounds of unreacted C₆₀ fullerenes, and/or about 0.001% toabout 1% dimer compounds of unreacted C₇₀ fullerenes, and/or about0.001% to about 1% dimer compounds of C₆₀ fullerene derivatives, and/orabout 0.001% to about 1% dimer compounds of C₇₀ fullerene derivatives.

In certain embodiments, the present invention relates to theaforementioned compositions, further comprising C60 and C70 bis-adductchemical derivatives; about 0.0001% to about 50% C60 and C70(cumulative); mono-adduct chemical derivatives of C60 and C70 in therange about 0.001% to about 50%; fullerenes higher in molecular weightthan C70 and derivatives of these fullerenes in the range about0.000001% to about 3%; oxides of C60 and C70 and oxides of C60 and C70derivatives in the range about 0.0001% to about 5%; and dimer compoundsof C60 and C70 and C60 and C70 derivatives in the range about 0.0001% toabout 5%. The ratio of C60 to C70 derivatives (to each other), whethermono or multi, can be anywhere from about 0.001% of each one; i.e.,about 99.999% [60]PCBM, about 0.001% [70]PCBM or about 0.001% [60]PCBM,about 99.999% [70]PCBM.

In certain other embodiments, the present invention relates to theaforementioned compositions, further comprising a C60 mono-adductchemical derivative; about 0.0001% to about 50% C60; multi-adducts ofthe C60 chemical derivative in the range of about 0.001% to about 30%;fullerenes higher in molecular weight than C70 and derivatives of thesefullerenes less than about 0.000001% about 1%; oxides of C60 and C70 andthe C60 and C70 derivatives about 0.0001% to about 1%.

In certain other embodiments, the present invention relates to theaforementioned compositions, further comprising a C70 mono-adductchemical derivative; about 0.0001% to about 50% C70; multi-adducts ofthe C70 chemical derivative in the range of about 0.001% to about 30%;fullerenes higher in molecular weight than C70 and derivatives of thesefullerenes less than about 0.000001% about 1%; oxides of C70 and C70 andthe C60 and C70 derivatives about 0.0001% to about 1%.

In certain embodiments, the present invention relates to theaforementioned compositions, further comprising less than about 0.0001%unreacted C₆₀ to about 50% unreacted C₆₀ and/or less than about 0.0001%unreacted C₇₀ to about 50% unreacted C₇₀.

In certain embodiments, the present invention relates to theaforementioned compositions, further comprising less than about 0.01%unreacted C₆₀ to about 10% unreacted C₆₀ and/or less than about 0.01%unreacted C₇₀ to about 10% unreacted C₇₀.

In certain embodiments, the present invention relates to theaforementioned compositions, further comprising less than about 0.1%unreacted C₆₀ to about 5% unreacted C₆₀ and/or less than about 0.1%unreacted C₇₀ to about 5% unreacted C₇₀.

In certain embodiments, the present invention relates to theaforementioned compositions further comprising about 0.001% to about 50%multi-adduct derivatives of C₆₀ and/or about 0.001% to about 50%multi-adduct derivatives of C₇₀.

In certain embodiments, the present invention relates to theaforementioned compositions further comprising about 0.01% to about 5%multi-adduct derivatives of C₆₀ and/or about 0.01% to about 5%multi-adduct derivatives of C₇₀.

In certain embodiments, the present invention relates to theaforementioned compositions further comprising about 0.01% to about 1%multi-adduct derivatives of C₆₀ and/or about 0.01% to about 1%multi-adduct derivatives of C₇₀.

In certain embodiments, the present invention relates to theaforementioned compositions, further comprising less than about 10% C₆₀mono-adduct chemical derivatives and/or less than about 10% C₇₀mono-adduct chemical derivatives.

In certain embodiments, the present invention relates to theaforementioned compositions, further comprising less than about 5% C₆₀mono-adduct chemical derivatives and/or less than about 5% C₇₀mono-adduct chemical derivatives.

In certain embodiments, the present invention relates to theaforementioned compositions, further comprising less than about 2% C₆₀mono-adduct chemical derivatives and/or less than about 2% C₇₀mono-adduct chemical derivatives.

In certain embodiments, the present invention relates to theaforementioned compositions, further comprising about 0.000001% to about3% unreacted fullerenes greater than C₇₀ and/or about 0.000001% to about3% fullerene derivatives greater than C₇₀.

In certain embodiments, the present invention relates to theaforementioned compositions, further comprising about 0.001% to about0.5% unreacted fullerenes greater than C₇₀ and/or about 0.001% to about0.5% fullerene derivatives greater than C₇₀.

In certain embodiments, the present invention relates to theaforementioned compositions, further comprising less than about 0.1%unreacted fullerenes greater than C₇₀ and/or less than about 0.1%fullerene derivatives greater than C₇₀.

Additional Process Embodiments

In certain embodiments, the present invention relates to the method ofsynthesizing a mixture of fullerene derivatives or a pure componentfullerene derivative by substituting a mixture of fullerenes for a purefullerene in a fullerene synthesis; varying the ratio of fullerenederivative content by using a purification technique.

In certain embodiments, the present invention relates to theaforementioned method where the purification method is filtration orelution over activated charcoal.

In certain embodiments, the present invention relates to theaforementioned method where the purification method is adsorption onactivated charcoal followed by filtration.

In certain embodiments, the present invention relates to theaforementioned method where the purification comprises multiple repeatedsteps.

In certain embodiments, the present invention relates to theaforementioned method where the purification method is preparatory scaleHPLC.

In certain embodiments, the present invention relates to theaforementioned method where the product obtained is substantially pure[60]derivative, [70]derivative, [76]derivative, [78]derivative, or[84]derivative

In certain embodiments, the present invention relates to theaforementioned method where the product obtained is any of claims theaforementioned compositions.

In certain embodiments, the present invention relates to theaforementioned method where the product comprises methanofullerenederivatives.

In certain embodiments, the present invention relates to theaforementioned method where product comprises PCBM derivatives.

In certain embodiments, the present invention relates to theaforementioned method where the product comprises ThCBM derivatives.

In certain embodiments, the present invention relates to theaforementioned method, where the fullerene derivatives consist of thesame addend, by first contacting the fullerene derivative mixturedissolved in a first solvent with activated carbon in the range of 0.01g/g (total) of fullerene derivative to 30 g/g (total) of fullerenederivative; eluting the supernatant to obtain a mixture higher inproportion relative to the original mixture in fullerene derivatives oflower molecular weight; contacting the activated carbon with a secondsolvent in which the fullerene derivatives are more soluble than thefirst solvent; eluting the second solvent to obtain a mixture higher inproportion relative to the original mixture in fullerene derivatives ofhigher molecular weight; repeating the above procedure as necessary toobtain the desired proportion of fullerene derivatives.

In certain embodiments, the present invention relates to theaforementioned method where the contacting procedure is passing thefullerene mixture over a bed of activated carbon, with or without asupporting medium.

In certain embodiments, the present invention relates to theaforementioned method where the contacting procedure is suspension ofthe activated carbon in the fullerene mixture by mixing;

In certain embodiments, the present invention relates to theaforementioned method where the proportion of activated carbon to gtotal of fullerene derivative mixture is in the range 0.1 g/g to 10 g/g.

In certain embodiments, the present invention relates to theaforementioned method where the proportion of activated carbon to gtotal of fullerene derivative mixture is 0.2 g/g to 5 g/g.

In certain embodiments, the present invention relates to theaforementioned method where the product is a mixture of C60 chemicalderivatives and C70 chemical derivatives in the proportion of 100:1 to1:100 percent molar.

In certain embodiments, the present invention relates to theaforementioned method where the product is 20:1 to 1:20 percent molar.

In certain embodiments, the present invention relates to theaforementioned method where the product is 5:1 to 1:5 percent molar.

In certain embodiments, the present invention relates to theaforementioned method where the proportion is altered so as to obtainsubstantially pure C60 derivative.

In certain embodiments, the present invention relates to theaforementioned method where the proportion is altered so as to obtainsubstantially pure C70 derivative.

In certain embodiments, the present invention relates to theaforementioned method where the proportion is altered so as to obtainderivatives of fullerenes higher than C70 of less than 0.5% molarrelative to total fullerene derivatives.

In certain embodiments, the present invention relates to theaforementioned method where the supporting medium is silica gel or sand.

Additional Composition Embodiments

-   -   In certain embodiments, the present invention relates to a        composition comprising: C60 and C70 chemical derivatives formed        by synthesis on a fullerene mixture, wherein the addend moieties        of the C60 and the C70 are the same; further comprised of    -   0.0001%-50% molar C60 and C70 (cumulative); multi-adduct        chemical derivatives of C60 and C70 in the range 0.001%-50%        molar; oxides of C60 and C70 and oxides of C60 and C70        derivatives in the range 0.0001%-5%;    -   dimer compounds of C60 and C70 and dimer compounds of C60 and        C70 derivatives in the range 0.0001%-5%; and    -   fullerenes higher in molecular weight than C70 and chemical        derivatives of fullerenes higher in molecular weight than C70        and oxides and dimers of fullerenes higher in molecular weight        than C70 and oxides and dimers of chemical derivatives of        fullerenes higher in molecular weight than C70 are in the        cumulative range of 0.000001%-3% molar.

In certain other embodiments, the present invention relates to acomposition comprising:

-   -   C60 and C70 in the range 0.01%-10%;    -   multi-adducts in the range 0.01%-5%;    -   fullerenes higher in molecular weight than C70 and derivatives        of these fullerenes in the range 0.001%-0.5%;    -   oxides of C60 and C70 and oxides of C60 and C70 derivatives in        the range 0.001%-2%; and    -   dimer compounds of C60 and C70 and C60 and C70 derivatives in        the range 0.001%-2%.

In certain other embodiments, the present invention relates to acomposition comprising:

-   -   C60 and C70 in the range 0.1%-5%;    -   multi-adducts in the range 0.01%-1%;    -   fullerenes higher in molecular weight than C70 and derivatives        of these fullerenes less than 0.1%;    -   oxides of C60 and C70 and oxides of C60 and C70 derivatives in        the range 0.01%-1%;    -   dimer compounds of C60 and C70 and C60 and C70 derivatives in        the range 0.01%-1%;

In certain embodiments, the present invention relates to:

-   -   C60 and C70 bis-adduct chemical derivatives;    -   0.0001%-50% C60 and C70 (cumulative);    -   mono-adduct chemical derivatives of C60 and C70 in the range        0.001%-50%;    -   fullerenes higher in molecular weight than C70 and derivatives        of these fullerenes in the range 0.000001%-3%;    -   oxides of C60 and C70 and oxides of C60 and C70 derivatives in        the range 0.0001%-5%; and    -   dimer compounds of C60 and C70 and C60 and C70 derivatives in        the range 0.0001%-5%.

In certain embodiments, the present invention relates to a compositionwhere rhe ratio of C60 to C70 derivatives (to each other), whether monoor multi, can be anywhere from 0.001% of each one; i.e., 99.999%[60]PCBM, 0.001% [70]PCBM or 0.001% [60]PCBM, 99.999% [70]PCBM.

In still other embodiments, the present invention relates to acomposition comprising:

A C60 mono-adduct chemical derivative;

-   -   0.0001%-50% C60;    -   multi-adducts of the C60 chemical derivative in the range        0.001%-30%;    -   fullerenes higher in molecular weight than C70 and derivatives        of these fullerenes less 0.000001%-1%; and    -   oxides of C60 and C70 and the C60 and C70 derivatives        0.0001%-1%.

EXAMPLES Example 1 Synthesis Information

Synthesis of Mixtures PCBM Derivatives ([C_(n)]PCBM)

Synthesis of PCBM derivatives was performed according to methodsdescribed in Hummelen et al. J. Org. Chem. 1995, 60, 532. Analysis byHPLC indicated about 74% [60]PCBM, 22% [70]PCBM, and 4% [>70]PCBM.Reduction of [>70] adducts may be performed by analytical or prep scaleHPLC, using a Cosmocil Buckyprep column, or activated carbon filtration.

In a typical methanofullerene synthesis, using arc-produced fullerenes,compositions of the product before any purification are approximately40% to 50% unreacted fullerenes, 40% to 50% [60] and [70] mono-adducts(˜9% bis, ˜1% tris), ≦1% other impurities (oxides of C₆₀ and thederivatives; dimers of C₆₀ and derivatives), 4% higher fullerene (>C₇₀)derivatives and unreacted fullerenes >C₇₀. Unreacted fullerenes may beremoved with a silica gel column. Higher fullerene derivatives may beremoved by analytical or prep scale HPLC, using a Cosmocil Buckyprepcolumn, or activated carbon filtration. The typical composition of thefinal product is 5% to 95%:95% to 5% [60]PCBM:[70]PCBM, <2% unreactedC₆₀ and C₇₀, <0.1% higher fullerene derivatives, <0.5% bis and othermulti-adducts, <1% oxide and dimers of unreacted fullerenes andfullerene derivatives.

Synthesis of Mixtures of ThCBM Derivatives [C_(n)]ThCBM

A mixture of 4.55 g of methyl 5-oxo-5-(thien-2-yl)-pentanoic acidp-tosyl hydrazone, 650 mg of sodium methoxide, and 10.1 g of commercialfullerene mix (71% C60, 23% C70, 6% C>70 by HPLC) in 1.0 L ofo-dichlorobenzene (ODCB) was heated to 90° C. under N2 for 17 h. Thecrude [Cn]ThCBM, as a mixture of [5,6] and [6,6] isomers, was isolatedby chromatography, as were the unreacted fullerenes (3.49 g).Irradiation of the crude [Cn]ThCBM in solution under N2 using a sodiumlamp gave full conversion to the [6,6] isomers. Chromatography (silicagel, toluene/cyclohexane 2:1 (v/v)) gave the ThCBMs. Precipitation usingmethanol from an ODCB solution and repeated washing using methanol andpentane gave, after drying at 50° C. in vacuo, 5.21 g of ThCBMs as ablack powder. Analysis by HPLC indicated about 74% [60]ThCBM, 23%[70]ThCBM, and 3% [>70]ThCBM. ¹H NMR (300 MHz, CDCl₃): δ 7.55-6.80(multiple signals, total 3H); 3.76-3.53 (multiple signals, total 3H);3.0-2.0 (multiple signals, total 6H) ppm. IR (KBr, cm-1): 2940; 2863;2328; 1735; 1430; 526. Reduction of [>70] adducts may be performed byanalytical or prep scale HPLC, using a Cosmocil Buckyprep column, oractivated carbon filtration.

Synthesis of Mixtures of Prato-Adducts of [C_(n)]Prato

Prato derivatives were prepared according to the general method of M.Prato and M. Maggini, Acc. Chem. Res. 1998, 31, 519-526.

Mixtures of a specific Prato compound as above ([60]Prato and [70]Pratoin this document) were prepared by using a mixture of 10.0 g ofcommercial fullerene mix (71% C₆₀, 23% C₇₀, 6% C_(>70) by HPLC), 1.50 gsarcosine, and 3.0 mL of 4-butoxybenzaldehyde in 1.0 L of ODCB washeated to 90-95° C. under N₂ for 21 h. The solvent was removed in vacuoand the reaction mixture was redissolved in a small amount of ODCB.Column chromatography (silica gel; p-xylene/heptane 2:1 (v/v)) gave theunreacted fullerenes (5.79 g) and the crude product (mixture ofmono-adducts). The crude product was redissolved in ODCB and furtherpurified by column chromatography (silica gel, o-xylene). The purified[Cn]Prato mixture was redissolved in ODCB and precipitated usingmethanol. Repeated washing using methanol and pentane gave, after dryingat 50° C. in vacuo, 3.85 g of product. Analysis by HPLC indicated about74% [60]-adduct, 22% [70]-adducts, and 4% [>70]-adducts. ¹H NMR (300MHz, CS₂+CDCl₃ 1:1 (v/v)): δ 7.80-6.60 (multiple signals, total 4H);5.05-4.60 (multiple signals, total 2H); 4.30-3.40 (multiple signals,total 3H); 3.10-2.20 (multiple signals, total 3H); 1.90-0.80 (multiplesignals, total 7H) ppm. Reduction of [>70] adducts may be performed aswell known in the art by analytical or prep scale HPLC, using a CosmocilBuckyprep column, or activated carbon filtration. n is 1 for themono-adduct and n is 2 for the bis-adduct.Methanofullerene Bis-Adducts

Methanofullerene bis-adducts, such as the ThCBM bis-adducts may beisolated from the reaction mixture as obtained from the synthesis ofThCBMs above (also see: L. M. Popescu et al, Appl. Phys. Lett. 2007, 89,213507), by further eluting the column used for the isolation of thecrude ThCBMs mono-adducts.

Additional References for Polymers

Fused or non-fused thiophene-ring containing polymers: An example ofsuch a polymer is poly(3-hexylthiophene-2,5-diyl), commonly known asP3HT. For use of this polymer in solar cells, see for example: L. M.Popescu et al., Appl. Phys. Lett. 2006, 89, 213507.

Fused or non-fused benzene-ring containing polymers: An example of sucha polymer ispoly(p-(2-(3,7-dimethyloctyloxy)-5-methoxy)-phenylenevinylene). For useof this polymer in solar cells, see for example: Shaheen et al., Appl.Phys. Lett. 2001, 78, 841.

Fused or non-fused pyrrole-ring containing polymers: An example of sucha polymer is polypyrrole (or polypyrrole) itself. For a method ofpreparation of this polymer, and subsequent characterization, see forexample T. F. Otero et al., Electrochimica Acta 1994, 39, 245.

Fused or non-fused thiadiazoline-ring containing polymers: An example ofsuch a polymer is poly(1,3,4-thiadiazole-co-thiophene), which has beenused in a field-effect transistor by Yamamoto and co-workers. See: T.Yamamoto et al., Macromol. Rapid. Commun. 2005, 26, 1214.

Fused or non-fused thiazoline-ring containing polymers: An example ofsuch a polymer is poly(4-nonylthiazole-co-thiophene-2,5-diyl). For thepreparation of this polymer, and the use in a field-effect transistor,see T. Yamamoto et al., Chem. Mater. 2004, 16, 4616.

Fused or non-fused pyrazine-ring containing polymers: An example of sucha polymer is poly(pyrazine-2,5-diyl), which has been described in T.Yamamoto et al., Polymer 2003, 44, 4487.

Example 2 Processing of Derivatized Fullerene Mixtures

Method 1:

Crude PCBM mixture, resulting from the synthesis using mixed fullerenes,was dissolved in p-xylene (10 g/L). The crude PCBM mixture typicallyconsists of 3-6% higher PCBM adducts ([>70]PCBM), 20-27% [70]PCBM and68-77% [60]PCBM, plus small amounts of unreacted fullerenes and traceamounts of fullerene oxides, fullerene derivative oxides, and dimers ofunreacted fullerenes and fullerene derivatives. Compositions may varydepending on fullerene production method, combustion produced fullerenestypically have higher percentages of C70 and higher fullerenes.

The mixed PCBMs are purified over a bed containing 2.5 grams activatedcharcoal (Merck charcoal activated GR for analysis, product number:102186) per gram PCBM, mixed with a supporting medium of Silica gel(Aldrich, Merck grade 9385, product number: 227196) in a 1:3.5 ratio(w/w), to allow for a better flow through the bed. The bed is preparedby mixing the activated charcoal and silica as dry powders, subsequentlythe mixed powder is suspended in p-xylene and poured into a glass columnequipped with a cotton plug and sand layer at the bottom. The bedmaterial is allowed to settle and is eluted until dry. Finally the cakeis covered with a small layer of sand.

The 10 g/l mixed PCBM solution in p-Xylene is filtered over the bed. Thecomplete filtrate can be collected as a [60] and [70]PCBM mixturewithout [>70]PCBM adducts. Alternatively the filtrate could befractionated into a first small pure [60]PCBM fraction to increase the[70]PCBM content of the overall product, followed by fractionsincreasing in [70]PCBM content. A fraction is obtained yieldingapproximately 76:23 [60]:[70]. Impurities ≦1% consists of C₆₀, C₇₀,[60]PCBM oxide and [70]PCBM oxide as determined by HPLC analysis(detection at 360 nm using Cosmocil Buckyprep column). Higher fullerenesand higher fullerene adducts are less than 0.1% cumulative.

Method 2:

Example 1 yields besides the pure product fractions as a side productseveral rinse fractions, obtained by further addition of p-xylene to thebed, which when combined have a general composition of 50-60% [60]PCBM,40-50% [70]PCBM and approximately 1% [>70]PCBM adducts. These combinedfractions can be re-dissolved in p-xylene (10 g/L) and purified again,as described is method one by using 3 g/g activated charcoal (Merckcharcoal activated GR for analysis, product number: 102186) per gramPCBM, mixed with Silica gel (Aldrich, Merck grade 9385, product number:227196) in a 1:3.5 ratio (w/w). The total volume of the solution plus3-5 times the initial volume as rinse fraction (p-xylene) is collectedas product fraction (without [>70]PCBM adducts)

The combined product fractions afforded a mixture of >99% [60] and[70]PCBM in a ratio close to 750:50 [60]:[70] as determined by HPLCanalysis at 360 nm. The <1% consists of C₆₀, C₇₀, [60]PCBM oxide and[70]PCBM oxide.

Method 3

The crude PCBM mixture as described in method 1 is dissolved in 10 g/Lp-xylene or toluene. 0.25 g/g Activated charcoal (Merck charcoalactivated Ph Eur, product number: 102555), is added to the stirredsolution. The solution is stirred for another 2-16 hours, filtered overa Buchner filter equipped with a paper filter plate. The filtratecontained 1.5-3.0% [>70]PCBM adducts. 0.25 g/g Activated charcoal wasadded to the filtrate and the procedure was repeated. After filteringthe [>70]PCBM content was 1.0-1.5%. This second filtrate was furtherpurified by a final filter step over an activated charcoal (1 g/g)(Merck charcoal activated Ph Eur)/silica gel cake (A.C.:SiO2 ratio 1:3.5(w/w)) as described in method 1, yielding less than 0.1% of derivativesof fullerenes higher than C70.

Method 4

The crude PCBM mixture as described in method 1 is dissolved in 10 g/Lp-xylene or toluene. 0.5 g/g Activated charcoal (Merck charcoalactivated, product number: 102555), is added to the stirred solution.The solution is stirred for another 2-16 hours, filtered over a Buchnerfilter equipped with a paper filter plate. The filtrate contained 0.5%[>70]PCBM adducts. 0.5 g/g Activated charcoal was added to the filtrateand the procedure was repeated. After filtering the [>70]PCBM contentwas 0.2%.

Method 5

8 g/g activated charcoal (Merck) mixed with silica gel in a 1:3.5 (w/w)ratio is used as described in Example 1. Crude PCBM mixture as describedin Example 1 is dissolved in toluene (10 g/L). Elute all toluene toobtain substantially pure [60]PCBM as a first product until the first[70]PCBM is collected. Change eluent to p-Xylene to elute [70]PCBM.Process yields 95% molar [70]PCBM relative to fullerene derivativefraction.

Example 3 Organic Photovoltaic Cell Preparation and Characterization

Solutions.

To study the device performance, blend solutions of P3HT:Fullerene(50:50 wt. %) were prepared in ortho-dichlorobenzene (ODCB) with aconcentration of 13 mg/ml. The solutions were prepared in a N₂atmosphere and rigorously stirred for more than 12 h on a hot platemaintained at 50° C.

Device Preparation.

The devices were prepared on indium tin oxide (ITO) covered glasssubstrates, which were cleaned using normal cleaning procedures andfinalized by exposing in a vacuum plasma cleaner for 20 minutes.Subsequently, a 60 nm thick layer ofpoly(3,4-ethylenedioxythiophene:poly(styrenesulfonate) (PEDOT:PSS) wasspin-coated from an aqueous dispersion under ambient conditions.Afterwards, the layer was dried in a lab oven at 200° C. for 5 minutes.The slow growth P3HT:Fullerene films were spun from ODCB solution on topof the PEDOT:PSS layer. Subsequently, the wet films were dried overnightat room temperature, in a closed Petri dish inside an N₂ glove box. Theaverage active layer thicknesses are about 230 nm. To complete thedevices, a Sm (5 nm)/Al (100 nm) top electrode was deposited by thermalevaporation.

Device Measurements.

The devices were illuminated by a white light halogen lamp with anoutput power of 100 mW/cm², determined by a calibrated silicon diodefrom Energy Research Centre of the Netherlands (ECN). The values werecorrected for the spectral mismatch.

INCORPORATION BY REFERENCE

All of the U.S. patents and U.S. patent application publications citedherein are hereby incorporated by reference.

EQUIVALENTS

Those skilled in the art will recognize, or be able to ascertain usingno more than routine experimentation, many equivalents to the specificembodiments of the invention described herein. Such equivalents areintended to be encompassed by the following claims.

We claim:
 1. A semiconductor, comprising a composition of formula (i),(ii), (iii), or (iv): (i) a composition comprising: a C₆₀ chemicalderivative selected from the group consisting of methanofullerenederivatives, PCBM derivatives, ThCBM derivatives, Prato derivatives,Bingel derivatives, diazoline derivatives, azafulleroid derivatives,ketolactam derivatives, and Diels-Alder derivatives; a C₇₀ chemicalderivative selected from the group consisting of methanofullerenederivatives, PCBM derivatives, ThCBM derivatives, Prato derivatives,Bingel derivatives, diazoline derivatives, azafulleroid derivatives,ketolactam derivatives, and Diels-Alder derivatives; wherein the C₆₀chemical derivative and the C₇₀ chemical derivative are both members ofthe same class of chemical derivatives; C₆₀ and C₇₀ in the cumulativerange of about 0% to about 50%; one or more C₆₀ bis-adduct chemicalderivative, one or more C₆₀ tris-adduct chemical derivative, one or moreC₇₀ bis-adduct chemical derivative, and one or more C₇₀ tris-adductchemical derivative in the cumulative range of about 0% to about 50%;one or more fullerene greater than C₇₀ and one or more chemicalderivative of fullerenes greater than C₇₀ in the cumulative range ofabout 0% to about 3%; one or more oxide of C₆₀, one or more oxide ofC₇₀, one or more oxide of C₆₀ chemical derivatives, and one or moreoxide of C₇₀ chemical derivatives in the cumulative range of about0.001% to about 5%; and one or more dimer of C₆₀, one or more dimer ofC₇₀, one or more dimer of C₆₀ chemical derivatives, and one or moredimer of C₇₀ chemical derivatives in the cumulative range of about 0% toabout 5%; (ii) a composition comprising: a C₆₀ chemical derivativeselected from the group consisting of bis-methanofullerene derivatives,bis-PCBM derivatives, bis-ThCBM derivatives, bis-Prato derivatives,bis-Bingel derivatives, bis-diazoline derivatives, bis-azafulleroidderivatives, bis-ketolactam derivatives, and bis-Diels Alderderivatives; a C₇₀ chemical derivative selected from the groupconsisting of bis-methanofullerene derivatives, bis-PCBM derivatives,bis-ThCBM derivatives, bis-Prato derivatives, bis-Bingel derivatives,bis-diazoline derivatives, bis-azafulleroid derivatives, bis-ketolactamderivatives, and bis-Diels Alder derivatives; wherein the C₆₀ chemicalderivative and the C₇₀ chemical derivative are both members of the sameclass of chemical derivatives; C₆₀ and C₇₀ in the cumulative the rangeof of about 0% to about 50%; one or more C₆₀ mono-adduct chemicalderivative, one or more C₆₀ tris-adduct chemical derivative, one or moreC₇₀ mono-adduct chemical derivative, and one or more C₇₀ tris-adductchemical derivative in the cumulative range of about 0% to about 50%;one or more fullerene greater than C₇₀ and one or more chemicalderivative of fullerenes greater than C₇₀ in the cumulative range ofabout 0% to about 3%; one or more oxide of C₆₀, one or more oxide ofC₇₀, one or more oxide of C₆₀ chemical derivatives, and one or moreoxide of C₇₀ chemical derivatives in the cumulative range of about0.001% to about 5%; and one or more dimer of C₆₀, one or more dimer ofC₇₀, one or more dimer of C₆₀ chemical derivatives, and one or moredimer of C₇₀ chemical derivatives in the cumulative range of about 0% toabout 5%; (iii) a composition comprising: a compound represented byformula I;

a compound represented by formula II;

wherein y is 1; A is a C₆₀ fullerene bonded to —C(X)(Y)— via amethano-bridge; A′ is a C₇₀ fullerene bonded to —C(X)(Y)— via amethano-bridge; X is optionally substituted aryl or aralkyl; Y is anoptionally substituted alkyl, optionally substituted cycloalkyl,optionally substituted heteroalkyl, optionally substitutedheterocycloalkyl, optionally substituted alkenyl, or optionallysubstituted aralkyl; C₆₀ and C₇₀ in the cumulative range of about 0% toabout 50%; one or more C₆₀ bis-adduct chemical derivative, one or moreC₆₀ tris-adduct chemical derivative, one or more C₇₀ bis-adduct chemicalderivative, and one or more C₇₀ tris-adduct chemical derivative are inthe cumulative range of about 0% to about 50%; one or more fullerenegreater than C₇₀ and one or more chemical derivative of fullerenesgreater than C₇₀ in the cumulative range of about 0% to about 3%; one ormore oxide of C₆₀, one or more oxide of C₇₀, one or more oxide of C₆₀chemical derivatives, and one or more oxide of C₇₀ chemical derivativesin the cumulative range of about 0.001% to about 5%; and one or moredimer of C₆₀, one or more dimer of C₇₀, one or more dimer of C₆₀chemical derivatives, and one or more dimer of C₇₀ chemical derivativesin the cumulative range of about 0% to about 5%; and (iv) a composition,comprising: a compound represented by formula I;

a compound represented by formula II;

wherein y is 2; A is a C₆₀ fullerene bonded to —C(X)(Y)— via amethano-bridge; A′ is a C₇₀ fullerene bonded to —C(X)(Y)— via amethano-bridge; X is optionally substituted aryl or aralkyl; Y is anoptionally substituted alkyl, optionally substituted cycloalkyl,optionally substituted heteroalkyl, optionally substitutedheterocycloalkyl, optionally substituted alkenyl, or optionallysubstituted aralkyl; C₆₀ and C₇₀ in the cumulative range of about 0% toabout 50%; one or more C₆₀ mono-adduct chemical derivative, one or moreC₆₀ tris-adduct chemical derivative, one or more C₇₀ mono-adductchemical derivative, and one or more C₇₀ tris-adduct chemical derivativeare in the cumulative range of about 0% to about 50%; one or morefullerene greater than C₇₀ and one or more chemical derivative offullerenes greater than C₇₀ in the cumulative range of about 0% to about3%; one or more oxide of C₆₀, one or more oxide of C₇₀, one or moreoxide of C₆₀ chemical derivatives, and one or more oxide of C₇₀ chemicalderivatives in the cumulative range of about 0.001% to about 5%; and oneor more dimer of C₆₀, one or more dimer of C₇₀, one or more dimer of C₆₀chemical derivatives, and one or more dimer of C₇₀ chemical derivativesin the cumulative range of about 0% to about 5%.
 2. The semiconductor ofclaim 1, further comprising a P-type semiconductor.
 3. The semiconductorof claim 2, wherein there are alternating layers of the N-typesemiconductor and the P-type semiconductor.
 4. The semiconductor ofclaim 2, wherein the N-type semiconductor and the P-type semiconductorare mixed to form a bulk heterojunction.
 5. The semiconductor of claim2, wherein the P-type semiconductor further comprises conjugatedpolymers, conjugated oligomers, conjugated molecules that are free ofrepeating units, or semi-conductive nano-particles.
 6. The semiconductorof claim 2, wherein the P-type semiconductor comprises fused ornon-fused thiophene-ring containing oligomers and polymers.
 7. Thesemiconductor of claim 2, wherein the P-type semiconductor comprisesfused or non-fused benzene-ring containing polymers.
 8. Thesemiconductor of claim 2, wherein the P-type semiconductor comprisesfused or non-fused pyrrole-ring containing polymers.
 9. Thesemiconductor of claim 2, wherein the P-type semiconductor comprisesfused or non-fused thiazoline-ring containing polymers.
 10. Thesemiconductor of claim 2, wherein the P-type semiconductor comprisesfused or non-fused thiadiazoline-ring containing polymers.
 11. Thesemiconductor of claim 2, wherein the P-type semiconductor comprisesfused or non-fused pyrazine-ring containing polymers.
 12. Thesemiconductor of claim 2, wherein the N-type semiconductor furthercomprises one or more additional N-type semiconductor other than thosedescribed in claim
 1. 13. A photodiode, comprising a photo-active layer,comprising at least one P-type semiconductor and an N-typesemiconductor, wherein the N-type semiconductor comprises asemiconductor of claim
 1. 14. The photodiode of claim 13, wherein theP-type semiconductor is selected from the group consisting of conjugatedpolymers, conjugated oligomers, conjugated molecules that are free ofrepeating units, semi-conductive nano-particles.
 15. The photodiode ofclaim 14, wherein the P-type semiconductor is selected from the groupcomprising fused or non-fused thiophene-ring containing oligomers andpolymers.
 16. The photodiode of claim 14, wherein the P-typesemiconductor is selected from the group comprising fused or non-fusedbenzene-ring containing polymers.
 17. The photodiode of claim 14,wherein the P-type semiconductor is selected from the group comprisingfused or non-fused pyrrole-ring containing polymers.
 18. The photodiodeof claim 14, wherein the P-type semiconductor is selected from the groupcomprising fused or non-fused thiazoline-ring containing polymers. 19.The photodiode of claim 14, wherein the P-type semiconductor is selectedfrom the group comprising fused or non-fused thiadiazoline-ringcontaining polymers.
 20. The photodiode of claim 14, wherein the P-typesemiconductor is selected from the group comprising fused or non-fusedpyrazine-ring containing polymers.
 21. The photodiode of claim 13,wherein the P-type semiconductor and the N-type semiconductor arepresent in the photo-active layer in the form of a mixture or asseparate sub-layers of one or more N-type semiconductor sub-layerscomprising the N-type semiconductor, and one or more P-typesemiconductor sub-layers, comprising the P-type semiconductor.
 22. Thephotodiode of claim 21, wherein the ratio of the weight of P-typesemiconductor to the ratio of the weight of N-type semiconductor is inthe range of 10:1 to 1:10.
 23. The photodiode of claim 21, wherein thephotodiode is used as a photovoltaic device.
 24. A photodetector orlight intensity meter, comprising a photodiode according to claim 21.25. An n-channel field effect transistor, comprising an N-typesemiconductor, wherein the N-type semiconductor comprises asemiconductor of claim
 1. 26. A p-channel field effect transistor,comprising a P-type semiconductor, wherein the P-type semiconductorcomprises a semiconductor of claim
 1. 27. A photovoltaic cell,photodetector, or organic field effect transistor comprising acomposition of formula (i), (ii), (iii), or (iv) (i) a compositioncomprising: a C₆₀ chemical derivative selected from the group consistingof methanofullerene derivatives, PCBM derivatives, ThCBM derivatives,Prato derivatives, Bingel derivatives, diazoline derivatives,azafulleroid derivatives, ketolactam derivatives, and Diels-Alderderivatives; a C₇₀ chemical derivative selected from the groupconsisting of methanofullerene derivatives, PCBM derivatives, ThCBMderivatives, Prato derivatives, Bingel derivatives, diazolinederivatives, azafulleroid derivatives, ketolactam derivatives, andDiels-Alder derivatives; wherein the C₆₀ chemical derivative and the C₇₀chemical derivative are both members of the same class of chemicalderivatives; C₆₀ and C₇₀ in the cumulative range of about 0% to about50%; one or more C₆₀ bis-adduct chemical derivative, one or more C₆₀tris-adduct chemical derivative, one or more C₇₀ bis-adduct chemicalderivative, and one or more C₇₀ tris-adduct chemical derivative in thecumulative range of about 0% to about 50%; one or more fullerene greaterthan C₇₀ and one or more chemical derivative of fullerenes greater thanC₇₀ in the cumulative range of about 0% to about 3%; one or more oxideof C₆₀, one or more oxide of C₇₀, one or more oxide of C₆₀ chemicalderivatives, and one or more oxide of C₇₀ chemical derivatives in thecumulative range of about 0.001% to about 5%; and one or more dimer ofC₆₀, one or more dimer of C₇₀, one or more dimer of C₆₀ chemicalderivatives, and one or more dimer of C₇₀ chemical derivatives in thecumulative range of about 0% to about 5%; (ii) a composition comprising:a C₆₀ chemical derivative selected from the group consisting ofbis-methanofullerene derivatives, bis-PCBM derivatives, bis-ThCBMderivatives, bis-Prato derivatives, bis-Bingel derivatives,bis-diazoline derivatives, bis-azafulleroid derivatives, bis-ketolactamderivatives, and bis-Diels Alder derivatives; a C₇₀ chemical derivativeselected from the group consisting of bis-methanofullerene derivatives,bis-PCBM derivatives, bis-ThCBM derivatives, bis-Prato derivatives,bis-Bingel derivatives, bis-diazoline derivatives, bis-azafulleroidderivatives, bis-ketolactam derivatives, and bis-Diels Alderderivatives; wherein the C₆₀ chemical derivative and the C₇₀ chemicalderivative are both members of the same class of chemical derivatives;C₆₀ and C₇₀ in the cumulative the range of of about 0% to about 50%; oneor more C₆₀ mono-adduct chemical derivative, one or more C₆₀ tris-adductchemical derivative, one or more C₇₀ mono-adduct chemical derivative,and one or more C₇₀ tris-adduct chemical derivative in the cumulativerange of about 0% to about 50%; one or more fullerene greater than C₇₀and one or more chemical derivative of fullerenes greater than C₇₀ inthe cumulative range of about 0% to about 3%; one or more oxide of C₆₀,one or more oxide of C₇₀, one or more oxide of C₆₀ chemical derivatives,and one or more oxide of C₇₀ chemical derivatives in the cumulativerange of about 0.001% to about 5%; and one or more dimer of C₆₀, one ormore dimer of C₇₀, one or more dimer of C₆₀ chemical derivatives, andone or more dimer of C₇₀ chemical derivatives in the cumulative range ofabout 0% to about 5%; (iii) a composition comprising: a compoundrepresented by formula I;

a compound represented by formula II;

wherein y is 1; A is a C₆₀ fullerene bonded to —C(X)(Y)— via amethano-bridge; A′ is a C₇₀ fullerene bonded to —C(X)(Y)— via amethano-bridge; X is optionally substituted aryl or aralkyl; Y is anoptionally substituted alkyl, optionally substituted cycloalkyl,optionally substituted heteroalkyl, optionally substitutedheterocycloalkyl, optionally substituted alkenyl, or optionallysubstituted aralkyl; C₆₀ and C₇₀ in the cumulative range of about 0% toabout 50%; one or more C₆₀ bis-adduct chemical derivative, one or moreC₆₀ tris-adduct chemical derivative, one or more C₇₀ bis-adduct chemicalderivative, and one or more C₇₀ tris-adduct chemical derivative are inthe cumulative range of about 0% to about 50%; one or more fullerenegreater than C₇₀ and one or more chemical derivative of fullerenesgreater than C₇₀ in the cumulative range of about 0% to about 3%; one ormore oxide of C₆₀, one or more oxide of C₇₀, one or more oxide of C₆₀chemical derivatives, and one or more oxide of C₇₀ chemical derivativesin the cumulative range of about 0.001% to about 5%; and one or moredimer of C₆₀, one or more dimer of C₇₀, one or more dimer of C₆₀chemical derivatives, and one or more dimer of C₇₀ chemical derivativesin the cumulative range of about 0% to about 5%; and (iv) a composition,comprising: a compound represented by formula I;

a compound represented by formula II;

wherein y is 2; A is a C₆₀ fullerene bonded to —C(X)(Y)— via amethano-bridge; A′ is a C₇₀ fullerene bonded to —C(X)(Y)— via amethano-bridge; X is optionally substituted aryl or aralkyl; Y is anoptionally substituted alkyl, optionally substituted cycloalkyl,optionally substituted heteroalkyl, optionally substitutedheterocycloalkyl, optionally substituted alkenyl, or optionallysubstituted aralkyl; C₆₀ and C₇₀ in the cumulative range of about 0% toabout 50%; one or more C₆₀ mono-adduct chemical derivative, one or moreC₆₀ tris-adduct chemical derivative, one or more C₇₀ mono-adductchemical derivative, and one or more C₇₀ tris-adduct chemical derivativeare in the cumulative range of about 0% to about 50%; one or morefullerene greater than C₇₀ and one or more chemical derivative offullerenes greater than C₇₀ in the cumulative range of about 0% to about3%; one or more oxide of C₆₀, one or more oxide of C₇₀, one or moreoxide of C₆₀ chemical derivatives, and one or more oxide of C₇₀ chemicalderivatives in the cumulative range of about 0.001% to about 5%; and oneor more dimer of C₆₀, one or more dimer of C₇₀, one or more dimer of C₆₀chemical derivatives, and one or more dimer of C₇₀ chemical derivativesin the cumulative range of about 0% to about 5%.
 28. A film fortime-gated holographic imaging, comprising a composition of formula (i),(ii), (iii), or (iv) (i) a composition comprising: a C₆₀ chemicalderivative selected from the group consisting of methanofullerenederivatives, PCBM derivatives, ThCBM derivatives, Prato derivatives,Bingel derivatives, diazoline derivatives, azafulleroid derivatives,ketolactam derivatives, and Diels-Alder derivatives; a C₇₀ chemicalderivative selected from the group consisting of methanofullerenederivatives, PCBM derivatives, ThCBM derivatives, Prato derivatives,Bingel derivatives, diazoline derivatives, azafulleroid derivatives,ketolactam derivatives, and Diels-Alder derivatives; wherein the C₆₀chemical derivative and the C₇₀ chemical derivative are both members ofthe same class of chemical derivatives; C₆₀ and C₇₀ in the cumulativerange of about 0% to about 50%; one or more C₆₀ bis-adduct chemicalderivative, one or more C₆₀ tris-adduct chemical derivative, one or moreC₇₀ bis-adduct chemical derivative, and one or more C₇₀ tris-adductchemical derivative in the cumulative range of about 0% to about 50%;one or more fullerene greater than C₇₀ and one or more chemicalderivative of fullerenes greater than C₇₀ in the cumulative range ofabout 0% to about 3%; one or more oxide of C₆₀, one or more oxide ofC₇₀, one or more oxide of C₆₀ chemical derivatives, and one or moreoxide of C₇₀ chemical derivatives in the cumulative range of about0.001% to about 5%; and one or more dimer of C₆₀, one or more dimer ofC₇₀, one or more dimer of C₆₀ chemical derivatives, and one or moredimer of C₇₀ chemical derivatives in the cumulative range of about 0% toabout 5%; (ii) a composition comprising: a C₆₀ chemical derivativeselected from the group consisting of bis-methanofullerene derivatives,bis-PCBM derivatives, bis-ThCBM derivatives, bis-Prato derivatives,bis-Bingel derivatives, bis-diazoline derivatives, bis-azafulleroidderivatives, bis-ketolactam derivatives, and bis-Diels Alderderivatives; a C₇₀ chemical derivative selected from the groupconsisting of bis-methanofullerene derivatives, bis-PCBM derivatives,bis-ThCBM derivatives, bis-Prato derivatives, bis-Bingel derivatives,bis-diazoline derivatives, bis-azafulleroid derivatives, bis-ketolactamderivatives, and bis-Diels Alder derivatives; wherein the C₆₀ chemicalderivative and the C₇₀ chemical derivative are both members of the sameclass of chemical derivatives; C₆₀ and C₇₀ in the cumulative the rangeof of about 0% to about 50%; one or more C₆₀ mono-adduct chemicalderivative, one or more C₆₀ tris-adduct chemical derivative, one or moreC₇₀ mono-adduct chemical derivative, and one or more C₇₀ tris-adductchemical derivative in the cumulative range of about 0% to about 50%;one or more fullerene greater than C₇₀ and one or more chemicalderivative of fullerenes greater than C₇₀ in the cumulative range ofabout 0% to about 3%; one or more oxide of C₆₀, one or more oxide ofC₇₀, one or more oxide of C₆₀ chemical derivatives, and one or moreoxide of C₇₀ chemical derivatives in the cumulative range of about0.001% to about 5%; and one or more dimer of C₆₀, one or more dimer ofC₇₀, one or more dimer of C₆₀ chemical derivatives, and one or moredimer of C₇₀ chemical derivatives in the cumulative range of about 0% toabout 5%; (iii) a composition comprising: a compound represented byformula I;

a compound represented by formula II

wherein y is 1; A is a C₆₀ fullerene bonded to —C(X)(Y)— via amethano-bridge; A′ is a C₇₀ fullerene bonded to —C(X)(Y)— via amethano-bridge; X is optionally substituted aryl or aralkyl; Y is anoptionally substituted alkyl, optionally substituted cycloalkyl,optionally substituted heteroalkyl, optionally substitutedheterocycloalkyl, optionally substituted alkenyl, or optionallysubstituted aralkyl; C₆₀ and C₇₀ in the cumulative range of about 0% toabout 50%; one or more C₆₀ bis-adduct chemical derivative, one or moreC₆₀ tris-adduct chemical derivative, one or more C₇₀ bis-adduct chemicalderivative, and one or more C₇₀ tris-adduct chemical derivative are inthe cumulative range of about 0% to about 50%; one or more fullerenegreater than C₇₀ and one or more chemical derivative of fullerenesgreater than C₇₀ in the cumulative range of about 0% to about 3%; one ormore oxide of C₆₀, one or more oxide of C₇₀, one or more oxide of C₆₀chemical derivatives, and one or more oxide of C₇₀ chemical derivativesin the cumulative range of about 0.001% to about 5%; and one or moredimer of C₆₀, one or more dimer of C₇₀, one or more dimer of C₆₀chemical derivatives, and one or more dimer of C₇₀ chemical derivativesin the cumulative range of about 0% to about 5%; and (iv) a composition,comprising: a compound represented by formula I;

a compound represented by formula II;

wherein y is 2; A is a C₆₀ fullerene bonded to —C(X)(Y)— via amethano-bridge; A′ is a C₇₀ fullerene bonded to —C(X)(Y)— via amethano-bridge; X is optionally substituted aryl or aralkyl; Y is anoptionally substituted alkyl, optionally substituted cycloalkyl,optionally substituted heteroalkyl, optionally substitutedheterocycloalkyl, optionally substituted alkenyl, or optionallysubstituted aralkyl; C₆₀ and C₇₀ in the cumulative range of about 0% toabout 50%; one or more C₆₀ mono-adduct chemical derivative, one or moreC₆₀ tris-adduct chemical derivative, one or more C₇₀ mono-adductchemical derivative, and one or more C₇₀ tris-adduct chemical derivativeare in the cumulative range of about 0% to about 50%; one or morefullerene greater than C₇₀ and one or more chemical derivative offullerenes greater than C₇₀ in the cumulative range of about 0% to about3%; one or more oxide of C₆₀, one or more oxide of C₇₀, one or moreoxide of C₆₀ chemical derivatives, and one or more oxide of C₇₀ chemicalderivatives in the cumulative range of about 0.001% to about 5%; and oneor more dimer of C₆₀, one or more dimer of C₇₀, one or more dimer of C₆₀chemical derivatives, and one or more dimer of C₇₀ chemical derivativesin the cumulative range of about 0% to about 5%.